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"uri": "/id/document/43170" } ] } } ], "eprint_status": "archive", "userid": 10051, "dir": "disk0/00/00/79/61", "datestamp": "2013-10-02 17:55:08", "lastmod": "2019-10-04 00:02:49", "status_changed": "2013-10-02 17:55:08", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "taylor.lenton@gmail.com", "id": "Lenton-Taylor-Nichole-Baker", "name": { "family": "Lenton", "given": "Taylor Nichole Baker" }, "show_email": "NO" } ] }, "title": "Bis(thiophenolate)pyridine Pincer Ligands and Trivalent Zirconocene Complexes Relevant to Earlv Transition Metal Polymerization Catalysts", "ispublished": "unpub", "full_text_status": "public", "keywords": "Pincer Ligands, Trivalent Zirconocene, Metallocene, Polypropylene", "abstract": "
Two major topics are covered: the first chapter is focused on the development of post-metallocene complexes for propylene polymerization. The second and third chapters investigate the consequences of diisobutylaluminum hydride (HAliBu2) additives in zirconocene based polymerization systems.
\r\n\r\nThe synthesis, structure, and solution behavior of early metal complexes with a new tridentate LX2 type ligand, bis(thiophenolate)pyridine ((SNS) = (2-C6H4S)2-2,6-C5H3N) are investigated. SNS complexes of Ti, Zr, and Ta having dialkylamido coligands were synthesized and structurally characterized. The zirconium complex, (SNS)Zr(NMe2)2, displays C2 symmetry in the solid state. Solid-state structures of tantalum complexes (SNS)Ta(NMe2)3 and (SNS)TaCl(NEt2)2 also display pronounced C2 twisting of the SNS ligand. 1D and 2D NMR experiments show that (SNS)Ta(NMe2)3 is fluxional with rotation about the Ta N(amide) bonds occurring on the NMR timescale. The fluxional behavior of (SNS)TaCl(NEt2)2 in solution was also studied by variable temperature 1H NMR. Observation of separate signals for the diastereotopic protons of the methylene unit of the diethylamide indicates that the complex remains locked on the NMR timescale in one diastereomeric conformation at temperatures below -50 \u00b0C.
\r\n\r\nReduction of Zr(IV) metallocenium cations with sodium amalgam (NaHg) produces EPR signals assignable to Zr(III) metallocene complexes. Thus, chloro-bridged heterobinuclear ansa-zirconocenium cation [((SBI))Zr(μ-Cl)2AlMe2]+B(C6F5)4¯ (SBI = rac-dimethylsilylbis(1-indenyl)), gives rise to an EPR signal assignable to the complex (SBI)ZrIII(μ-Cl)2AlMe2, while (SBI)ZrIII-Me and (SBI)ZrIII(-H)2AliBu2 are formed by reduction of [(SBI)Zr(μ-Me)2AlMe2]+B(C6F5)4¯ and [(SBI)Zr(μ-H)3(AliBu2)2]+B(C6F5)4¯, respectively. These products are also formed, along with (SBI)ZrIII-iBu and [(SBI)ZrIII]+ AlR4¯ when (SBI)ZrMe2 reacts with HAliBu2, eliminating isobutane en route to the Zr(III) complex. Studies concerning the interconversion reactions between these and other (SBI)Zr(III) complexes and reaction mechanisms involved in their formation are also reported.
\r\n\r\nThe addition of HAliBu2 to precatalyst [(SBI)Zr(\u00b5-H)3(AliBu2)2]+ significantly slows the polymerization of propylene and changes the kinetics of polymerization from 1st to 2nd order with respect to propylene. This is likely due to competitive inhibition by HAliBu2. When the same reaction is investigated using [(nBuCp)2Zr(μ-H)3(AliBu2)2]+, hydroalumination between propylene and HAliBu2 is observed instead of propylene polymerization.
\r\n", "date": "2014", "date_type": "degree", "id_number": "CaltechTHESIS:09242013-191401866", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:09242013-191401866", "related_url": { "items": [ { "description": "Article adapted for ch. 2", "type": "doi", "url": "http://dx.doi.org/10.1021/om300789h" }, { "description": "Article adapted for ch. 3", "type": "doi", "url": "http://dx.doi.org/10.1021/ja403170u" } ] }, "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "deposited_by": "Taylor Lenton", "deposited_on": "2013-10-02 17:55:08", "doi": "10.7907/FPP5-0461", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "jeb@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "agapie@caltech.edu", "id": "Agapie-T", "name": { "family": "Agapie", "given": "Theodor" }, "role": "chair" }, { "email": "stolz@caltech.edu", "id": "Stoltz-B-M", "name": { "family": "Stoltz", "given": "Brian M." }, "role": "member" }, { "email": "gcfu@caltech.edu", "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "role": "member" }, { "email": "jeb@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "2013-09-10", "gradofc_approval_date": "2013-10-01", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "2014", "author_list": "Lenton, Taylor Nichole Baker", "advisor_list": "Bercaw, John E.", "comittee_list": "Agapie, Theodor; Stoltz, Brian M.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/8486", "eprint_id": 8486, "rev_number": 22, "documents": [ { "id": "/id/document/50115", "doc_id": 50115, "rev_number": 4, "files": [ { "id": "/id/file/145162", "fileid": 145162, "datasetid": "document", "objectid": 50115, "filename": "Senior Thesis Final Report_Iva Rreza.pdf", "mime_type": "application/pdf", "hash": "795dae80cba4532c4365441f07c2cef1", "hash_type": "MD5", "filesize": 3739172, "mtime": "2014-06-05 21:17:48", "url": "/8486/1/Senior Thesis Final Report_Iva Rreza.pdf" } ], "eprint_id": 8486, "pos": 1, "placement": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", 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"media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/50115" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/50115" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/50115" } ] } } ], "eprint_status": "archive", "userid": 10285, "dir": "disk0/00/00/84/86", "datestamp": "2014-06-06 18:34:52", "lastmod": "2022-08-02 21:44:50", "status_changed": "2014-06-06 18:34:52", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "irreza@caltech.edu", "id": "Rreza-Iva", "name": { "family": "Rreza", "given": "Iva" }, "show_email": "NO" } ] }, "title": "Development of Tantalum Phenoxy-Imine Compounds for Selective Ethylene Oligomerization", "ispublished": "unpub", "full_text_status": "public", "keywords": "dimerization, organometallics, tantalum, phenoxy-imine", "abstract": "The development of catalysts that selectively oligomerize light olefins for uses in polymers and fuels remains of interest to the petrochemical and materials industry. For this purpose, two tantalum compounds, (FI)TaMe2Cl2 and (FI)TaMe4, implementing a previously reported phenoxy-imine (FI) ligand framework, have been synthesized and characterized with NMR spectroscopy and X-ray crystallography. When tested for ethylene oligomerization catalysis, (FI)TaMe2Cl2 was found to dimerize ethylene when activated with Et2Zn or EtMgCl, and (FI)TaMe4 dimerized ethylene when activated with B(C6F5)3, both at room temperature.", "date": "2014", "date_type": "degree", "id_number": "CaltechTHESIS:06052014-141223337", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:06052014-141223337", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "BP", "grant_number": "JEB.XC2-1-BP.XC2" } ] }, "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "local_group": { "items": [ "Senior Undergraduate Thesis Prize" ] }, "suggestions": "Restricted to Caltech community only until 6 June 2015. Released Jan. 4, 2016. ", "deposited_by": "Iva Rreza", "deposited_on": "2014-06-06 18:34:52", "doi": "10.7907/YDBK-V594", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "senior_major", "thesis_advisor": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "name": { "family": "None", "given": "None" } } ] }, "thesis_degree": "BS", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "2014-06-06", "thesis_awards": "Library Friends Senior Thesis Prize Finalist, 2014", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "2014", "author_list": "Rreza, Iva", "advisor_list": "Bercaw, John E.", "comittee_list": "None, None" }, { "id": "https://thesis.library.caltech.edu/id/eprint/7962", "eprint_id": 7962, "rev_number": 44, "documents": [ { "id": "/id/document/43222", "doc_id": 43222, "rev_number": 4, "files": [ { "id": "/id/file/128922", "fileid": 128922, "datasetid": "document", "objectid": 43222, "filename": "RCKThesis_TitleIntro.pdf", "mime_type": "application/pdf", "hash": "d660525f8ac6a25f43f4dcf52c6bf81f", "hash_type": "MD5", "filesize": 236396, "mtime": "2013-09-26 16:30:03", "url": "/7962/1/RCKThesis_TitleIntro.pdf" } ], "eprint_id": 7962, "pos": 1, "placement": 2, "mime_type": "application/pdf", "format": "application/pdf", "format_desc": "Title-Abstract-ToC", "language": "en", "security": "public", "license": "other", 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"http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/43258" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/43258" } ] } } ], "eprint_status": "archive", "userid": 5881, "dir": "disk0/00/00/79/62", "datestamp": "2015-01-06 22:28:13", "lastmod": "2019-10-04 00:02:50", "status_changed": "2015-01-06 22:28:13", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "rcklet@gmail.com", "id": "Klet-Rachel-Christine", "name": { "family": "Klet", "given": "Rachel Christine" }, "show_email": "NO" } ] }, "title": "Carbon-Carbon Bond Forming Reactions from Bis(carbene)-Platinum(II) Complexes and Olefin Polymerization and Oligomerization using Group 4 Post-Metallocene Complexes ", "ispublished": "unpub", "full_text_status": "public", "keywords": "Olefin polymerization, carbon-carbon bond formation, regioirregular polypropylene", "abstract": "A long-standing challenge in transition metal catalysis is selective C\u2013C bond coupling of simple feedstocks, such as carbon monoxide, ethylene or propylene, to yield value-added products. This work describes efforts toward selective C\u2013C bond formation using early- and late-transition metals, which may have important implications for the production of fuels and plastics, as well as many other commodity chemicals.
\r\n\r\nThe industrial Fischer-Tropsch (F-T) process converts synthesis gas (syngas, a mixture of CO + H2) into a complex mixture of hydrocarbons and oxygenates. Well-defined homogeneous catalysts for F-T may provide greater product selectivity for fuel-range liquid hydrocarbons compared to traditional heterogeneous catalysts. The first part of this work involved the preparation of late-transition metal complexes for use in syngas conversion. We investigated C\u2013C bond forming reactions via carbene coupling using bis(carbene)platinum(II) compounds, which are models for putative metal\u2013carbene intermediates in F-T chemistry. It was found that C\u2013C bond formation could be induced by either (1) chemical reduction of or (2) exogenous phosphine coordination to the platinum(II) starting complexes. These two mild methods afforded different products, constitutional isomers, suggesting that at least two different mechanisms are possible for C\u2013C bond formation from carbene intermediates. These results are encouraging for the development of a multicomponent homogeneous catalysis system for the generation of higher hydrocarbons.
\r\n\r\nA second avenue of research focused on the design and synthesis of post-metallocene catalysts for olefin polymerization. The polymerization chemistry of a new class of group 4 complexes supported by asymmetric anilide(pyridine)phenolate (NNO) pincer ligands was explored. Unlike typical early transition metal polymerization catalysts, NNO-ligated catalysts produce nearly regiorandom polypropylene, with as many as 30-40 mol % of insertions being 2,1-inserted (versus 1,2-inserted), compared to <1 mol % in most metallocene systems. A survey of model Ti polymerization catalysts suggests that catalyst modification pathways that could affect regioselectivity, such as C\u2013H activation of the anilide ring, cleavage of the amine R-group, or monomer insertion into metal\u2013ligand bonds are unlikely. A parallel investigation of a Ti\u2013amido(pyridine)phenolate polymerization catalyst, which features a five- rather than a six-membered Ti\u2013N chelate ring, but maintained a dianionic NNO motif, revealed that simply maintaining this motif was not enough to produce regioirregular polypropylene; in fact, these experiments seem to indicate that only an intact anilide(pyridine)phenolate ligated-complex will lead to regioirregular polypropylene. As yet, the underlying causes for the unique regioselectivity of anilide(pyridine)phenolate polymerization catalysts remains unknown. Further exploration of NNO-ligated polymerization catalysts could lead to the controlled synthesis of new types of polymer architectures.
\r\n\r\nFinally, we investigated the reactivity of a known Ti\u2013phenoxy(imine) (Ti-FI) catalyst that has been shown to be very active for ethylene homotrimerization in an effort to upgrade simple feedstocks to liquid hydrocarbon fuels through co-oligomerization of heavy and light olefins. We demonstrated that the Ti-FI catalyst can homo-oligomerize 1-hexene to C12 and C18 alkenes through olefin dimerization and trimerization, respectively. Future work will include kinetic studies to determine monomer selectivity by investigating the relative rates of insertion of light olefins (e.g., ethylene) vs. higher \u03b1-olefins, as well as a more detailed mechanistic study of olefin trimerization. Our ultimate goal is to exploit this catalyst in a multi-catalyst system for conversion of simple alkenes into hydrocarbon fuels.
\r\n", "date": "2014", "date_type": "degree", "id_number": "CaltechTHESIS:09262013-092439684", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:09262013-092439684", "related_url": { "items": [ { "description": "Article adapted for ch. 2", "type": "doi", "url": "http://dx.doi.org/10.1021/om300733h" }, { "description": "Article adapted for ch. 3", "type": "doi", "url": "http://dx.doi.org/ 10.1039/c2cc32806b" } ] }, "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "deposited_by": "Rachel Klet", "deposited_on": "2015-01-06 22:28:13", "doi": "10.7907/WRTW-6Z10", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "agapie@caltech.edu", "id": "Agapie-T", "name": { "family": "Agapie", "given": "Theodor" }, "role": "chair" }, { "email": "jal@its.caltech.edu", "id": "Labinger-J-A", "name": { "family": "Labinger", "given": "Jay A." }, "role": "member" }, { "email": "reisman@caltech.edu", "id": "Reisman-S-E", "name": { "family": "Reisman", "given": "Sarah E." }, "role": "member" }, { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "member" }, { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "2013-08-19", "gradofc_approval_date": "2013-10-01", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "2014", "author_list": "Klet, Rachel Christine", "advisor_list": "Bercaw, John E.", "comittee_list": "Agapie, Theodor; Labinger, Jay A.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/7225", "eprint_id": 7225, "rev_number": 30, "documents": [ { "id": "/id/document/15318", "doc_id": 15318, "rev_number": 4, "files": [ { "id": "/id/file/100103", "fileid": 100103, "datasetid": "document", "objectid": 15318, "filename": "MSW_Thesis.pdf", "mime_type": "application/pdf", "filesize": 15482561, "mtime": "2012-12-26 04:45:17", "url": "/7225/1/MSW_Thesis.pdf" } ], "eprint_id": 7225, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "format_desc": "Doctoral Dissertation", "language": "en", "security": "public", "license": "other", "main": "MSW_Thesis.pdf", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "final", "relation": { "items": [ { "type": "http://eprints.org/relation/hasVolatileVersion", "uri": "/id/document/28189" }, { "type": "http://eprints.org/relation/haspreviewThumbnailVersion", "uri": "/id/document/28189" }, { "type": "http://eprints.org/relation/hasVersion", "uri": "/id/document/28189" } ] } }, { "id": "/id/document/28189", "doc_id": 28189, "rev_number": 2, "files": [ { "id": "/id/file/100101", "fileid": 100101, "datasetid": "document", "objectid": 28189, "filename": "preview.png", "mime_type": "image/png", "hash": "6ccc990d24e67f391a2191d062b7e001", "hash_type": "MD5", "filesize": 23874, "mtime": "2012-12-26 04:45:17", "url": "/7225/2/preview.png" } ], "eprint_id": 7225, "pos": 2, "placement": 2, "mime_type": "image/png", "format": "image/png", "language": "en", "security": "public", "license": "other", "main": "preview.png", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/15318" }, { "type": "http://eprints.org/relation/ispreviewThumbnailVersionOf", "uri": "/id/document/15318" }, { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/15318" } ] } }, { "id": "/id/document/127674", "doc_id": 127674, "rev_number": 1, "files": [ { "id": "/id/file/373110", "fileid": 373110, "datasetid": "document", "objectid": 127674, "filename": "indexcodes.txt", "mime_type": "text/plain", "hash": "66352c0abdc40593f7110898438a886a", "hash_type": "MD5", "filesize": 43279, "mtime": "2021-06-24 01:57:49", "url": "/7225/3/indexcodes.txt" } ], "eprint_id": 7225, "pos": 3, "placement": 3, "mime_type": "text/plain", "format": "other", "format_desc": "Generate index codes conversion from application/pdf to indexcodes", "language": "en", "security": "public", "license": "other", "main": "indexcodes.txt", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/15318" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/15318" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/15318" } ] } } ], "eprint_status": "archive", "userid": 9610, "dir": "disk0/00/00/72/25", "datestamp": "2012-10-30 17:47:58", "lastmod": "2019-10-03 23:57:05", "status_changed": "2012-10-30 17:47:58", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "mattswinston@gmail.com", "id": "Winston-Matthew-Steven", "name": { "family": "Winston", "given": "Matthew Steven" }, "show_email": "NO" } ] }, "title": "Chemistry of PNP Bis(phosphide) Pincer Ligands and Palladium(II) Dimers as Robust, Versatile Precatalysts for Olefin Isomerization, Oligomerization, and Oxidation", "ispublished": "unpub", "full_text_status": "public", "keywords": "Organometallic chemistry, organic chemistry, inorganic chemistry", "abstract": "The first half of this thesis details the synthesis and coordination chemistry of a very unusual pyridine-linked bis(secondary phosphine) pincer ligand system. Despite the highly nucleophilic phosphide donors, this dianionic system is an unexpectedly poor pincer ligand. Crystallographic and DFT studies reveal that both phosphide-metal \u03c3- and \u03c0-bonding is compromised by long metal-phosphorus bonds, which result in significant distortions to the chelate ring. The neutral ligand coordinates readily \u03ba2 (via phosphines) to late metals, such as palladium(II), affording P-chirogenic diastereomers. Crystallographic and spectroscopic analysis of a series of palladium(II) dihalides stabilized by this bis(phosphine) indicate that one diastereomer is enthalpically favored, while the other more structurally versatile diastereomer is favored entropically. There is also evidence of an interesting phosphine epimerization pathway assisted by the non-coordinated pyridine ring.
\r\n\r\nEthylene polymerization and ethylene/1-hexene copolymerization activities of several zirconium(IV) and vanadium(III) polymerization precatalysts supported by heterocycle-linked bis(phenolate) ligands are also discussed. Activities as high as 106 g PE/(mol x h) were observed, but only the vanadium catalyst incorporates comonomer, albeit with low efficiency (<1 mol%).
\r\n\r\nFinally, catalytic applications of air- and water-tolerant bis(\u03bc-hydroxy) palladium(II) dimers have been investigated. Mechanistic studies show that this precatalyst can oxygenate olefins via a Wacker-type mechanism upon dimer dissociation. In the absence of stoichiometric oxidant, the resulting palladium(II) hydride intermediate can then isomerize and oligomerize olefins with turnover numbers at room temperature as high as 2100/h and 600/h, respectively. We also show that the catalyst is insensitive to water and air, so that olefin isomerization and oligomerization can be carried out on the benchtop in the absence of activators. In the presence of excess tert-butylhydroperoxide, Wacker-type behavior is favored, and neither isomerization nor oligomerization is observed. These dimers can also catalyze the aerobic dehydrogenation of cyclohexene to benzene with relatively low turnover numbers (1/h). Nevertheless, mechanistic studies indicate a C-H activation/\u03b2-hydride elimination sequence that does not involve an allylic-activated species.
\r\n", "date": "2013", "date_type": "degree", "id_number": "CaltechTHESIS:10052012-153447918", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:10052012-153447918", "related_url": { "items": [ { "type": "doi", "url": "http://dx.doi.org/10.1021/om100775g" }, { "type": "doi", "url": "http://dx.doi.org/10.1002/anie.201206215" } ] }, "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "deposited_by": "Matthew Winston", "deposited_on": "2012-10-30 17:47:58", "doi": "10.7907/GES9-N146", "alt_title": { "items": [ "Palladium(II) Dimers as Robust, Versatile Precatalysts for Olefin Isomerization, Oligomerization, and Oxidation" ] }, "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" }, { "email": "jal@caltech.edu", "id": "Labinger-J-A", "name": { "family": "Labinger", "given": "Jay A." }, "role": "co-advisor" } ] }, "thesis_committee": { "items": [ { "email": "reisman@caltech.edu", "id": "Reisman-S-E", "name": { "family": "Reisman", "given": "Sarah E." }, "role": "chair" }, { "email": "rhg@caltech.edu", "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "role": "member" }, { "email": "jpeters@caltech.edu", "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "role": "member" }, { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "2012-10-01", "gradofc_approval_date": "2012-10-24", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "2013", "author_list": "Winston, Matthew Steven", "advisor_list": "Bercaw, John E. and Labinger, Jay A.", "comittee_list": "Reisman, Sarah E.; Grubbs, Robert H.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/6627", "eprint_id": 6627, "rev_number": 31, "documents": [ { "id": "/id/document/13533", "doc_id": 13533, "rev_number": 5, "files": [ { "id": "/id/file/87715", "fileid": 87715, "datasetid": "document", "objectid": 13533, "filename": "Oblad2012Thesis.pdf", "mime_type": "application/pdf", "filesize": 4885105, "mtime": "2012-12-26 04:38:35", "url": "/6627/1/Oblad2012Thesis.pdf" } ], "eprint_id": 6627, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "format_desc": "Full Thesis", "language": "en", "security": "public", "license": "other", "main": "Oblad2012Thesis.pdf", 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"media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/15264" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/15264" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/15264" } ] } } ], "eprint_status": "archive", "userid": 6530, "dir": "disk0/00/00/66/27", "datestamp": "2011-10-19 18:51:10", "lastmod": "2019-10-03 23:53:01", "status_changed": "2012-09-07 16:24:38", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "paul.oblad@gmail.com", "id": "Oblad-Paul-Frederick", "name": { "family": "Oblad", "given": "Paul Frederick" }, "show_email": "NO" } ] }, "title": "Toward the Upgrading of Hydrocarbons: Synthesis, Characterization, and Reactivity of Platinum and Palladium Complexes", "ispublished": "unpub", "full_text_status": "public", "keywords": "platinum ; palladium ; organometallics ; C-H activation ; oligomerization ; hydrocarbon functionalization", "abstract": "Herein, hydroxyl-dimers of platinum and palladium supported by diimine ligands have been prepared and studied. It was found that they are capable of activating allylic, benzylic, and aromatic carbon-hydrogen bonds. The kinetics of the C-H activation of cyclohexene with the platinum system and of indene with the palladium system were studied. In each case the rate-limiting step was found to be associative substitution. The catalytic dehydrogenation of cyclohexene to benzene with the palladium hydroxyl-dimer was investigated. The chemical oxidation of the \u03b73-organometallic products synthesized via C-H activation of cyclohexene and indene with platinum and palladium, respectively, was explored. Treatment of these products with strong halogenating oxidants resulted in the liberation of halogenated substrates and bridging halide metal complexes. Uncharged platinum and palladium polypyrazoleborate complexes were synthesized and characterized. The kinetics of the degenerative ligand exchange of DMSO with palladium methyl DMSO complexes ligated with a polypyrazoleborate or a diimine ligand were studied and it was found that the associative substitution mechanism through which the diimine ligated complexes proceeds was unavailable to the polypyrazoleborate palladium complex. In the polypyrazoleborate system ligand exchange proceeded through a dissociative mechanism. The C-H activation substrate scope of the platinum and palladium hydroxyl-dimers was further explored. The diimine platinum hydroxyl-dimer was found to activate an allylic C-H bond in cyclopentene and form an \u03b73-cyclopentenyl complex when heated with acid and dilute stoichiometric amounts of cyclopentene. Conversely, dehydrogenation of cyclopentene to a platinum-bound \u03b75-cyclopentadiene resulted from the treatment of the platinum hydroxyl-dimer with super-stoichiometric amounts of cyclopentene at room temperature. This difference in reactivity with the same substrate may be due to the relative reactivities of allylic versus homoallylic C-H bonds. Further evidence of a homoallylic C-H activation mechanism was demonstrated by treating the diimine platinum hydroxyl-dimer with neo-hexene to form a cyclometalated neo-hexenyl platinum complex. The diimine palladium hydroxyl-dimer was also found to catalytically oligomerize and isomerize olefins. Furthermore, the catalytic activity was supported by the presence of oxygen and stable in the presence of water. Most likely the oligomerization proceeded through a palladium hydride that can decompose to palladium(0) complex, which can be reoxidized by oxygen. The photochemical oxidation of platinum complexes with Ru(bipy)_3^(2+) was also investigated. Finally, the coordination chemistry of the tris(triphenylphosphino)silyl ligand was explored with cobalt, ruthenium, nickel, and platinum. ", "date": "2012", "date_type": "degree", "id_number": "CaltechTHESIS:08292011-105052667", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:08292011-105052667", "related_url": { "items": [ { "type": "doi", "url": "http://dx.doi.org/10.1021/ja076740q" }, { "type": "doi", "url": "http://dx.doi.org/10.1002/anie.200804455" }, { "type": "doi", "url": "http://dx.doi.org/10.1021/om900678z" }, { "type": "doi", "url": "http://dx.doi.org/10.1021/ic801855y" } ] }, "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "deposited_by": "Paul Oblad", "deposited_on": "2011-10-19 18:51:10", "doi": "10.7907/ZEHM-9S69", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "co-advisor" }, { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "co-advisor" } ] }, "thesis_committee": { "items": [ { "email": "nslewis@caltech.edu", "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan Saul" }, "role": "chair" }, { "email": "mo@its.caltech.edu", "id": "Okumura-M", "name": { "family": "Okumura", "given": "Mitchio" }, "role": "member" }, { "email": "winklerj@caltech.edu", "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "Jay Richmond" }, "role": "member" }, { "email": "jal@its.caltech.edu", "id": "Labinger-J-A", "name": { "family": "Labinger", "given": "Jay A." }, "role": "member" }, { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" }, { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "2011-08-26", "gradofc_approval_date": "2011-10-12", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "2012", "author_list": "Oblad, Paul Frederick", "advisor_list": "Bercaw, John E. and Gray, Harry B.", "comittee_list": "Lewis, Nathan Saul; Okumura, Mitchio; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/6755", "eprint_id": 6755, "rev_number": 25, "documents": [ { "id": "/id/document/14042", "doc_id": 14042, "rev_number": 5, "files": [ { "id": "/id/file/90322", "fileid": 90322, "datasetid": "document", "objectid": 14042, "filename": "Tonks_Thesis_Corrected.pdf", "mime_type": "application/pdf", "filesize": 10940169, "mtime": "2012-12-26 04:39:37", "url": "/6755/1/Tonks_Thesis_Corrected.pdf" } ], "eprint_id": 6755, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": "Tonks_Thesis_Corrected.pdf", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "final", "relation": { "items": [ { "type": "http://eprints.org/relation/hasVolatileVersion", "uri": "/id/document/27752" }, { "type": "http://eprints.org/relation/haspreviewThumbnailVersion", "uri": "/id/document/27752" }, { "type": "http://eprints.org/relation/hasVersion", "uri": "/id/document/27752" } ] } }, { "id": "/id/document/27752", "doc_id": 27752, "rev_number": 2, "files": [ { "id": "/id/file/90320", "fileid": 90320, "datasetid": "document", "objectid": 27752, "filename": "preview.png", "mime_type": "image/png", "hash": "bbcd285ed79a5150d4734476da1f9162", "hash_type": "MD5", "filesize": 21439, "mtime": "2012-12-26 04:39:37", "url": "/6755/2/preview.png" } ], "eprint_id": 6755, "pos": 2, "placement": 2, "mime_type": "image/png", "format": "image/png", "language": "en", "security": "public", "license": "other", "main": "preview.png", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/14042" }, { "type": "http://eprints.org/relation/ispreviewThumbnailVersionOf", "uri": "/id/document/14042" }, { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/14042" } ] } }, { "id": "/id/document/127136", "doc_id": 127136, "rev_number": 1, "files": [ { "id": "/id/file/372570", "fileid": 372570, "datasetid": "document", "objectid": 127136, "filename": "indexcodes.txt", "mime_type": "text/plain", "hash": "5f92d39d256484b4a5a15fe2c06a96b7", "hash_type": "MD5", "filesize": 39282, "mtime": "2021-06-24 01:28:15", "url": "/6755/3/indexcodes.txt" } ], "eprint_id": 6755, "pos": 3, "placement": 3, "mime_type": "text/plain", "format": "other", "format_desc": "Generate index codes conversion from application/pdf to indexcodes", "language": "en", "security": "public", "license": "other", "main": "indexcodes.txt", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/14042" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/14042" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/14042" } ] } } ], "eprint_status": "archive", "userid": 7321, "dir": "disk0/00/00/67/55", "datestamp": "2012-05-16 20:51:26", "lastmod": "2019-10-03 23:53:55", "status_changed": "2012-05-16 20:51:26", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "iantonks@gmail.com", "id": "Tonks-Ian-Albert", "name": { "family": "Tonks", "given": "Ian Albert" }, "show_email": "NO" } ] }, "title": "Fundamental Studies of Early Transition Metal-Ligand Multiple Bonds: Structure, Electronics, and Catalysis", "ispublished": "unpub", "full_text_status": "public", "keywords": "Niobium, Tantalum, Titanium, Triple Bonds, Hydrazide, Hydroamination, Polymerization, C-H Activation, Nitrogen Activation", "abstract": "Two major topics are covered: the first section is focused on the structure, electronics, stoichiometric reactivity and catalysis of nonmetallocene early transition metal complexes that often contain metal-ligand multiple bonds (Chapters 2-4); the second section is dedicated to the development of hydrazide(2-) ligands for group 5 elements, which were heretofore unexplored as ligands for group 5 (Chapters 5-6).
\r\n\r\nA series of tantalum imido and amido complexes supported by a pyridine linked bis(phenolate) (ONO) ligand has been synthesized. Characterization of these complexes via X ray crystallography reveals both Cs and C2 binding modes of the bis(phenolate)pyridine ligand. DFT calculations and molecular orbital analyses of the complexes have revealed that the preference for Cs symmetric ligand binding is a result of Ta-O \u03c0 bonding: in cases where Ta-O \u03c0 bonding is overridden by stronger Ta N \u03c0 bonding, C2 symmetric ligand binding is preferred because this is the lowest energy geometric conformation.
\r\n\r\nTitanium and zirconium complexes supported by a related pyridine bis(anilide) ligand (NNN = pyridine 2,6 bis(N-mesitylanilide)) have been synthesized. The ligand geometry of these complexes is dictated solely by chelate ring strain rather than metal-ligand \u03c0-bonding. These complexes were tested as propylene polymerization precatalysts, with most complexes giving low to moderate activities (10^2-10^4 g/mol*h) for the formation of polypropylene.
\r\n\r\n(ONO)TiX2 complexes are highly active precatalysts for the intermolecular hydroamination of internal alkynes with primary arylamines and some alkylamines. (ONO)TiBn2 also cyclotrimerizes dimethylacetylene. During the cyclotrimerization reaction the Ti(IV) precatalyst is reduced to Ti(II), which is the active species for catalysis. The mechanism of formation of TiII has been investigated and an (ONO)Ti(II) species has been trapped by ethylene and crystallographically characterized.
\r\n\r\nHydrazide complexes (dme)TaCl3(NNPh2) and (dme)NbCl3(NNPh2) (dme = 1,2 dimethoxyethane) were synthesized. Unlike the corresponding imido derivatives, (dme)TaCl3(NNPh2) is dark blue due to an LMCT that has been lowered in energy as a result of an N\u03b1-N\u03b2 antibonding interaction that raises the HOMO. Reaction of (dme)TaCl3(NNPh2) with a variety of neutral, mono and dianionic ligands generates the corresponding ligated complexes retaining the k-1 bound [TaNNPh2] moiety.
\r\n\r\nFurthermore, a series of colorful terminal hydrazide complexes of the type (dme)MCl3(NNR2) (M = Nb, Ta; R = alkyl or aryl) or (MeCN)WCl4(NNR2) have been synthesized. Perturbing the electronic environment of the \u03b2 nitrogen significantly impacts the lowest-energy charge transition in these complexes, and in the W complexes leads to metal based reduction. The photophysics of these complexes highlights the importance of the difference in reduction potential between metal centers, and could lead to differences in ligand- and/or metal-based redox chemistry in early transition metal hydrazidos, especially in the context of N2 fixation.
\r\n\r\nFinally, the hydroxy-bridged dimer [(COD)IrOH]2 (COD = 1,5-cyclooctadiene) cleanly C-H activates indene and cyclopentadiene to form (COD)Ir(\u03b73-indenyl) and (COD)Ir(\u03b75-C5H5), respectively. The kinetics of the formation of (COD)Ir(\u03b73-indenyl) has been investigated, and the mechanism involves coordination of indene to the dimeric [(COD)IrOH]2 followed by rate determining C-H activation from the dimer-indene unit.
\r\n", "date": "2012", "date_type": "degree", "id_number": "CaltechTHESIS:12192011-112528810", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:12192011-112528810", "related_url": { "items": [ { "type": "doi", "url": "http://dx.doi.org/10.1021/ic802234x" }, { "type": "doi", "url": "http://dx.doi.org/10.1021/ic1004193" } ] }, "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "USDOE Office of Basic Energy Sciences", "grant_number": "DE-FG03-85ER13431" } ] }, "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "deposited_by": "Ian Tonks", "deposited_on": "2012-05-16 20:51:26", "doi": "10.7907/FYGA-KK18", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "chair" }, { "email": "stoltz@caltech.edu", "id": "Stoltz-B-M", "name": { "family": "Stoltz", "given": "Brian M." }, "role": "member" }, { "email": "rhg@caltech.edu", "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "role": "member" }, { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "2011-12-06", "gradofc_approval_date": "2012-05-16", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "2012", "author_list": "Tonks, Ian Albert", "advisor_list": "Bercaw, John E.", "comittee_list": "Gray, Harry B.; Stoltz, Brian M.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/6579", "eprint_id": 6579, "rev_number": 29, "documents": [ { "id": "/id/document/13394", "doc_id": 13394, "rev_number": 4, "files": [ { "id": "/id/file/86826", "fileid": 86826, "datasetid": "document", "objectid": 13394, "filename": "ECW_Thesis_Chapter1_Through_Chapter4.pdf", "mime_type": "application/pdf", "filesize": 1693397, "mtime": "2012-12-26 04:38:07", "url": "/6579/1/ECW_Thesis_Chapter1_Through_Chapter4.pdf" } ], "eprint_id": 6579, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "format_desc": "Ch.1-4", "language": "en", "security": "public", "license": "other", "main": 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"edwardcharles.weintrob@gmail.com", "id": "Weintrob-Edward-Charles", "name": { "family": "Weintrob", "given": "Edward Charles" }, "show_email": "YES" } ] }, "title": "Synthesis, Characterization, and Reactivity Studies of Pyridine Bis(anilide) Iron Complexes", "ispublished": "unpub", "full_text_status": "public", "keywords": "Iron, pincer ligand, C-H activation, azide, anilide", "abstract": "The unifying concept within this thesis is the investigation of pyridine bis(anilide) (NNN) iron complexes. Within this topic, chapter 1 speaks to the motivation behind studying these complexes, and how they relate to problems within iron catalysis in general. Chapter 2 introduces the general ligand design and the features which are thought to give unique and desirable properties to the complexes derived from it. The mesityl susbstituted ligand [MesNNN]H2 and subsequently ferrous ([MesNNN]Fe(THF)) and ferric ([MesNNN]FeI and ([MesNNN]Fe)2O) complexes are synthesized. The properties of the complexes are investigated using a variety of characterization techniques. Such techniques include paramagnetic 1H NMR spectroscopy, X-ray crystallography, Evans method, cyclic voltammetry, DFT calculations, and UV-vis spectrscopy. A detailed explanation of the challenges and solutions involved in using paramagnetic NMR are discussed. Crystallographic data indicate that the ligand framework confers a quite unusual geometry about the iron center, especially for the ferrous derivative [MesNNN]Fe(THF). The factors involved in this geometry are discussed, and DFT calculations supplement this discussion. Chapter 3 focuses on the reactivity of the iron complexes. Various oxidants and reductants were employed which interconvert the iron derivatives in chapter 2. Organometallic derivatives [MesNNN]FeR (R = hydride, alkyl, aryl) were not accessible, likely due to homolytic processes. L ligand exchange for [MesNNN]Fe(THF) was investigated. Ethylene reversibly binds, while cyclohexene does not. Trimethylphosphonium methylidene displaces THF to generate [MesNNN]FeCH2PMe3. Although the I oxidation state was accessible for [MesNNN]Fe(THF) electrochemically, attempts to chemically produce Fe I complexes based on the NNN ligand led to multiple products. Chapter 4 focuses on the intramolecular C-H activation of [MesNNN]Fe(THF) with RN3 to afford [MesNNN-NHR]Fe (R = SiMe3, adamantyl). The kinetics of the reaction with Me3SiN3 was investigated in detail, and a mechanism was proposed. Iron complexes based on the pincer ligands [tBuNNN] and [ONO] were investigated. ", "date": "2012", "date_type": "degree", "id_number": "CaltechTHESIS:08112011-151147364", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:08112011-151147364", "related_url": { "items": [ { "type": "doi", "url": "http://dx.doi.org/10.1021/ic900083s" } ] }, "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "USDOE Office of Basic Energy Sciences", "grant_number": "DE-FG03-85ER13431" }, { "agency": "Moore Foundation" } ] }, "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "deposited_by": "Edward Weintrob", "deposited_on": "2011-08-25 18:42:59", "doi": "10.7907/M1Y4-RM69", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "rhg@caltech.edu", "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "role": "chair" }, { "email": "stoltz@caltech.edu", "id": "Stoltz-B-M", "name": { "family": "Stoltz", "given": "Brian M." }, "role": "member" }, { "email": "jal@its.caltech.edu", "id": "Labinger-J-A", "name": { "family": "Labinger", "given": "Jay A." }, "role": "member" }, { "email": "jpeters@caltech.edu", "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "role": "member" }, { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "2011-07-28", "gradofc_approval_date": "2011-08-18", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. 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methane to methanol and methanol to higher hydrocarbons. The first section is on understanding the catalytic formation of methanol from methane, with specific interest in using gold (Au). While this transformation is known to occur catalytically, very little is understood about how it happens. To study this reaction, well-defined Au-complexes were synthesized and reactions relevant to the possible catalytic cycles were examined. In doing so, the first simple Au(III)-monoalkyl complex was generated and characterized: (Idipp)AuI2Me, where Idipp = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene). Kinetics experiments demonstrated that the complex reductively eliminates methyl iodide, which is relevant to the functionalization step in CH activation. At low concentrations of iodide, the reductive elimination happens faster, from an unobserved 3-coordinate intermediate. However, at high iodide concentrations, the pathway is still consistent with reductive elimination, but from a 5-coordinate intermediate. This is in contrast to the related platinum-system, as well as to density functional theory calculations done on the Au-system.
\r\n \r\nThe second section studies the C-H activation step alone by close examination of the microscopic reverse: protonation of a metal-alkyl. It had previously been noted that the observed kinetic isotope effects (KIEs) were unusually high for the protonolysis of a few Pd complexes and one Pt complex. It was hypothesized that these high KIEs and involvement of quantum mechanical tunneling may indicate a change in the mechanism of the protonolysis reaction, from protonation at the metal center and reductive coupling to direct protonation of the M-Me bond. The experiments described here were designed to explicitly test this theory and demonstrated that no correlation can be made between mechanism and tunneling.
\r\n\r\nThe third section is focused on the study of the conversion of methanol to highly branched alkanes that make good fuel additives, namely 2,2,3-trimethylbutane (triptane), amidst other alkanes, olefins, and aromatics. Catalyzed by ZnI2 or InI3 at high temperatures, the reaction is hydrogen deficient: aromatics are formed as unsaturated by-products necessary for alkane generation. While the product distributions are somewhat different for the two different catalysts, the general mechanism is the same. While typical InI3 reactions generate more alkanes, more aromatics, and fewer olefins than ZnI2 reactions, longer reaction times and higher temperatures make the ZnI2 reaction look like the InI3 profile. Furthermore, InI3 can activate alkanes; it was found that InI3 can \u201cupgrade\u201d other alkanes with methanol. Notably, a 1:1 mixture of 2,3-dimethylbutane and methanol can be converted into triptane with good selectivity and little aromatic formation; ZnI2 can carry out similar chemistry at higher temperatures. Quantification of the iodine-containing products in each reaction mixture was attempted because of its relevance to the system\u2019s industrial viability and found that these concentrations were significantly higher than would be acceptable in an industrial setting.
\r\n", "date": "2011-02-14", "date_type": "degree", "id_number": "CaltechTHESIS:02272011-102614437", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:02272011-102614437", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "deposited_by": "Valerie Scott", "deposited_on": "2011-02-28 20:08:12", "doi": "10.7907/P0A0-JV28", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" }, { "email": "jal@caltech.edu", "id": "Labinger-J-A", "name": { "family": "Labinger", "given": "Jay A." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "stoltz@caltech.edu", "id": "Stoltz-B-M", "name": { "family": "Stoltz", "given": "Brian M." }, "role": "chair" }, { "email": "jal@caltech.edu", "id": "Labinger-J-A", "name": { "family": "Labinger", "given": "Jay A." }, "role": "member" }, { "email": "gray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "member" }, { "email": "barton@caltech.edu", "id": "Barton-J-K", "name": { "family": "Barton", "given": "Jacqueline K." }, "role": "member" }, { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "2011-02-14", "gradofc_approval_date": "2011-02-28", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "2011", "author_list": "Scott, Valerie J.", "advisor_list": "Bercaw, John E. and Labinger, Jay A.", "comittee_list": "Stoltz, Brian M.; Labinger, Jay A.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/6197", "eprint_id": 6197, "rev_number": 48, "documents": [ { "id": "/id/document/11732", "doc_id": 11732, "rev_number": 5, "files": [ { "id": "/id/file/78053", "fileid": 78053, "datasetid": "document", "objectid": 11732, "filename": "AJMM_Thesis_Chapter1_through_Chapter4.pdf", "mime_type": "application/pdf", "filesize": 15365055, "mtime": "2012-12-26 04:32:27", "url": "/6197/1/AJMM_Thesis_Chapter1_through_Chapter4.pdf" } ], "eprint_id": 6197, "pos": 1, "placement": 2, "mime_type": "application/pdf", "format": "application/pdf", "format_desc": "TOC and ch.1-4", "language": "en", "security": 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borane, carbon monoxide, hydrogenation, rhenium", "note": "Ch. 1: \r\nAdapted in part from: \r\nWest, N. M.; Miller, A. J. M.; Labinger, J. A.; Bercaw, J. E. Coord. Chem. Rev. 2010, In press. Copyright 2010 Elsevier B.V. (http://dx.doi.org/10.1016/j.ccr.2010.08.019)\r\n\r\nCh. 3: \r\nAdapted in part from:\r\nMiller, A. J. M.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 2008, 130, 11874. Copyright 2008 American Chemical Society (http://dx.doi.org/10.1021/ja805108z)\r\n\u2013and\u2013\r\nMiller, A. J. M.; Labinger, J. A.; Bercaw, J. E. Organometallics 2010, 29, 4499. Copyright 2010 American Chemical Society (http://dx.doi.org/10.1021/om100638d)\r\n\r\nCh. 4:\r\nAdapted in part from:\r\nMiller, A. J. M.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 2010, 132, 3301. Copyright 2010 American Chemical Society (http://dx.doi.org/10.1021/ja100574n)\r\n\r\nCh.6:\r\nAdapted in part from:\r\nMiller, A. J. M.; Bercaw, J. E. Chem. Commun. 2010, 46, 1709. Copyright 2010 Royal Chemical Society (http://dx.doi.org/10.1039/B925659H)", "abstract": "Two major themes are presented, in roughly chronological order: the synthesis and characterization of photoluminescent copper complexes are described, followed by studies on the selective conversion of synthesis gas (CO and H2) to oxygenates. With the latter comprising the majority of the work, it is the subject of the introductory Chapter 1. In Chapter 2, the photoluminescent copper chemistry is introduced, and the synthesis and photophysics of monomeric amidophosphine complexes of copper is presented. The copper complexes are exceptional luminophores, with quantum efficiency up to 70% and lifetimes up to 150 \u03bcs. In Chapter 3, homogeneous CO hydrogenation is pursued using a strategy reliant on the incorporation of pendent Lewis acidic groups into the secondary coordination sphere of a metal carbonyl complex. This design feature promotes facile C\u2013H and C\u2013C bond formation, with transition metal hydrides as the hydrogen source. A structure-function study investigating the specific role of the Lewis acid determined that thefirst C\u2013H bond formation is not particularly sensitive to the acid, whereas the second C\u2013H bond formation and C\u2013C coupling are both highly sensitive to the length of the tether between the metal and the borane. In Chapter 4, this chemistry is extended to utilize dihydrogen directly as a reductant, in a \"frustrated Lewis pair\" (FLP) mechanism. A strong phosphazene base is too bulky to interact with the pendent borane, but can heterolytically cleave dihydrogen in concert with the borane to generate a borohydride that transforms the carbonyl ligands into a metal-bound C2 organic fragment. In Chapter 5, Lewis acidic boranes are again employed as promoters of reductive chemistry, this time for CO2 reduction. The same late transition metal hydrides that were employed for CO reduction, such as [HNi(dmpe)2][BF4] (dmpe = 1,2-bis(dimethylphosphino)ethane), are able to reduce CO2 gas when used in concert with the appropriate borane, affording a borane-formate adduct. In Chapter 6, the \"frustrated Lewis pair\" concept is extended to a different problem: the dehydrogenation of amine-boranes, which are candidates for hydrogen storage applications. Treatment of amine-boranes with the FLP tBu3P/B(C6F5)3 effects rapid and quantitative transfer of H2 from the amine-borane, forming cyclic aminoborane products along with [tBu3PH][HB(C6F5)3]. Appendices are provided, including early work on Br\u00f8nsted acid-assisted CO reduction, speciation of trialkylborohydrides, tabulating NMR impurities in deuterated solvents of interest to the organometallic chemist, and crystallographic tables.\r\n", "date": "2011", "date_type": "degree", "id_number": "CaltechTHESIS:12072010-151616905", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:12072010-151616905", "related_url": { "items": [ { "description": "Article adapted for ch. 1", "type": "doi", "url": "http://dx.doi.org/10.1016/j.ccr.2010.08.019" }, { "description": "Article adapted for ch. 3", "type": "doi", "url": "http://dx.doi.org/10.1021/ja805108z" }, { "description": "Article adapted for ch. 3", "type": "doi", "url": "http://dx.doi.org/10.1021/om100638d" }, { "description": "Article adapted for ch. 4", "type": "doi", "url": "http://dx.doi.org/10.1021/ja100574n" }, { "description": "Article adapted for ch. 6", "type": "doi", "url": "http://dx.doi.org/10.1039/B925659H" } ] }, "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "deposited_by": "Alexander Miller", "deposited_on": "2011-02-11 18:36:06", "doi": "10.7907/SPH6-R695", "alt_title": { "items": [ "Emissive Monocopper Amidophosphine Complexes", "Lewis Acid-Assisted Reductive Coupling of Carbon Monoxide" ] }, "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "stoltz@caltech.edu", "id": "Stoltz-B-M", "name": { "family": "Stoltz", "given": "Brian M." }, "role": "chair" }, { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" }, { "email": "rhg@caltech.edu", "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "role": "member" }, { "email": "agapie@caltech.edu", "id": "Agapie-T", "name": { "family": "Agapie", "given": "Theodor" }, "role": "member" }, { "email": "jal@caltech.edu", "id": "Labinger-J-A", "name": { "family": "Labinger", "given": "Jay A." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "2010-11-12", "gradofc_approval_date": "2011-02-09", "thesis_awards": "The Herbert Newby McCoy Award, 2011.", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "2011", "author_list": "Miller, Alexander James Minden", "advisor_list": "Bercaw, John E.", "comittee_list": "Stoltz, Brian M.; Bercaw, John E.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/6181", "eprint_id": 6181, "rev_number": 33, "documents": [ { "id": "/id/document/11779", "doc_id": 11779, "rev_number": 7, "files": [ { "id": "/id/file/77716", "fileid": 77716, "datasetid": "document", "objectid": 11779, "filename": "SMBThesis.pdf", "mime_type": "application/pdf", "filesize": 4608701, "mtime": "2012-12-26 04:32:15", "url": "/6181/1/SMBThesis.pdf" } ], "eprint_id": 6181, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": "SMBThesis.pdf", "media_duration": "0", "media_aspect_ratio": "0", 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"http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/11779" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/11779" } ] } } ], "eprint_status": "archive", "userid": 2955, "dir": "disk0/00/00/61/81", "datestamp": "2011-02-18 00:19:39", "lastmod": "2019-10-09 17:07:05", "status_changed": "2011-02-18 00:19:39", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "sbaldwinner@gmail.com", "id": "Baldwin-Steven-M", "name": { "family": "Baldwin", "given": "Steven M." }, "show_email": "NO" } ] }, "title": "Investigation of the Role of Hydrides in Zirconocene Catalyzed Olefin Polymerization", "ispublished": "unpub", "full_text_status": "public", "keywords": "polymerization; hydride; zirconocene", "abstract": "The structure and reactivity of zirconocene hydrides in the presence of aluminum alkyls is investigated for both neutral species and cationic species. Unbridged zirconocene dichlorides react with HAliBu2 to yield trihydride dialuminum clusters of the general formula (RnC5H5-n)2Zr(\u03bc-H)3(AliBu2)3(\u03bc-Cl)2. Bridged zirconocenes instead predominantly yield a dihydride monoaluminum cluster of the general form Me2E(RnC5H4-n)2Zr(Cl)(\u03bc-H)2AliBu2 where E = Si or C. For tert-butyl substituted zirconocenes the terminal Cl is replaced by a H. It is shown that steric factors dictate which hydride is formed.
\r\n\r\nA single type of cationic trihydride dialuminum cluster of general formula [(RnC5H4-n)2Zr(\u03bc-H)3(AliBu2)+] is formed for all zirconocene hydrides upon addition of [Ph3C][B(C6F5)4] regardless of which class of neutral hydride was formed. For {(SBI)Zr} and {(Me2Si)2(C5H3)2Zr} the resulting cations were crystallographically characterized where SBI stands for Me2Si(indenyl)2. [(SBI)Zr(\u03bc-H)3(AliBu2)]+ reacts with propene to make isotactic polypropene while the Me-substituted analogue [(SBI)Zr(\u03bc-H)3(AliMe2)]+ is a catalyst for hydroalumination. These trihydride cations are shown to be dormant species in polymerization reactions. [(SBI)Zr(\u03bc-H)3(AliBu2)]+ is identified as the hydride observed by Babushkin and Brintzinger (Babushkin, D. E.; Brintzinger, H. H. Chem. Eur. J. 2007, 13, 5294) upon addition of AliBu3 or HAliBu2 to a mixture of (SBI)ZrCl2 and methylaluminoxane.
\r\n", "date": "2011", "date_type": "degree", "id_number": "CaltechTHESIS:11182010-211348487", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:11182010-211348487", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "deposited_by": "Steven Baldwin", "deposited_on": "2011-02-18 00:19:39", "doi": "10.7907/P2XG-AD12", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "chair" }, { "email": "stoltz@caltech.edu", "id": "Stoltz-B-M", "name": { "family": "Stoltz", "given": "Brian M." }, "role": "member" }, { "email": "jpeters@caltech.edu", "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "role": "member" }, { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "2010-11-22", "gradofc_approval_date": "2011-02-17", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "2011", "author_list": "Baldwin, Steven M.", "advisor_list": "Bercaw, John E.", "comittee_list": "Gray, Harry B.; Stoltz, Brian M.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/5405", "eprint_id": 5405, "rev_number": 26, "documents": [ { "id": "/id/document/8928", "doc_id": 8928, "rev_number": 4, "files": [ { "id": "/id/file/55268", "fileid": 55268, "datasetid": "document", "objectid": 8928, "filename": "GSC_Thesis.pdf", "mime_type": "application/pdf", "filesize": 5390378, "mtime": "2012-12-26 03:19:07", "url": "/5405/1/GSC_Thesis.pdf" } ], "eprint_id": 5405, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": "GSC_Thesis.pdf", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "final", "relation": { "items": [ { "type": "http://eprints.org/relation/hasVolatileVersion", "uri": "/id/document/25094" }, { "type": "http://eprints.org/relation/haspreviewThumbnailVersion", "uri": "/id/document/25094" }, { "type": "http://eprints.org/relation/hasVersion", "uri": "/id/document/25094" } ] } }, { "id": "/id/document/9346", "doc_id": 9346, "rev_number": 3, "files": [ { "id": "/id/file/204924", "fileid": 204924, "datasetid": "document", "objectid": 9346, "filename": "Chen_George_S_2010.PDF", "mime_type": "application/pdf", "filesize": 42473, "mtime": "2016-08-22 21:18:20", "url": "/5405/2/Chen_George_S_2010.PDF" } ], "eprint_id": 5405, "pos": 2, "format": "application/pdf", "language": "en", "security": "internal", "license": "other", "main": "Chen_George_S_2010.PDF", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "approvalform" }, { "id": "/id/document/25094", "doc_id": 25094, "rev_number": 2, "files": [ { "id": "/id/file/55266", "fileid": 55266, "datasetid": "document", "objectid": 25094, "filename": "preview.png", "mime_type": "image/png", "hash": "f4b11dd32f58ca711c3a4d678dba8700", "hash_type": "MD5", "filesize": 9081, "mtime": "2012-12-26 03:19:07", "url": "/5405/3/preview.png" } ], "eprint_id": 5405, "pos": 3, "placement": 3, "mime_type": "image/png", "format": "image/png", "language": "en", "security": "public", "license": "other", "main": "preview.png", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/8928" }, { "type": "http://eprints.org/relation/ispreviewThumbnailVersionOf", "uri": "/id/document/8928" }, { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/8928" } ] } }, { "id": "/id/document/125431", "doc_id": 125431, "rev_number": 1, "files": [ { "id": "/id/file/370865", "fileid": 370865, "datasetid": "document", "objectid": 125431, "filename": "indexcodes.txt", "mime_type": "text/plain", "hash": "1844668cdf7993f0342237911fc8339c", "hash_type": "MD5", "filesize": 23623, "mtime": "2021-06-24 00:10:31", "url": "/5405/4/indexcodes.txt" } ], "eprint_id": 5405, "pos": 4, "placement": 4, "mime_type": "text/plain", "format": "other", "format_desc": "Generate index codes conversion from application/pdf to indexcodes", "language": "en", "security": "public", "license": "other", "main": "indexcodes.txt", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/8928" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/8928" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/8928" } ] } } ], "eprint_status": "archive", "userid": 530, "dir": "disk0/00/00/54/05", "datestamp": "2009-12-23 16:53:33", "lastmod": "2019-11-08 18:07:40", "status_changed": "2009-12-23 16:53:33", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "georgec@caltech.edu", "id": "Chen-George-Shuxiong", "name": { "family": "Chen", "given": "George Shuxiong" }, "show_email": "NO" } ] }, "title": "Mechanisms of C-H Bond Activation by Platinum(II)", "ispublished": "unpub", "full_text_status": "public", "keywords": "C-H activation", "abstract": "The rates of C\u2013H bond activation for various alkanes by [(N\u2013N)PtII(CH\u2083)(TFE-d\u2083)]\u207a (N\u2013N = Ar\u2013N=C(CH\u2083)\u2013C(CH\u2083)=N\u2013Ar; Ar = 3,5-di-tert-butylphenyl; TFE-d\u2083 = CF\u2083CD\u2082OD) were studied. Both linear and cyclic alkanes give the corresponding [(N\u2013N)PtII(H)(alkene)]\u207a cation. Second-order rate constants for cycloalkane activation (CnH2n) are proportional to the size of the ring (k ~ n). For cyclohexane, the deuterium kinetic isotope effect (kH/kD) of 1.28(5) is consistent with the proposed rate determining alkane coordination to form a C\u2013H \u03c3 complex. Comparing the relative rates of cyclic and linear alkanes indicates that the platinum center is relatively unselective with respect to different C\u2013H bonds: the rate constants (per C\u2013H bond) for the substrates examined all fall into a narrow range, and there does not appear to be any significant preference for either primary or secondary C\u2013H bonds.
\r\n\r\nThe protonolysis of platinum(II) methyl complexes was investigated by both experiment and computation. Experimental results showed that protonolysis of (COD)PtII(CH\u2083)\u2082 (COD = 1,5 \u2013 cyclooctadiene) by trifluoroacetic acid gave abnormally large (greater than 10) kinetic isotope effects (kH/kD) at room temperature and higher. The temperature dependence of kH/kD for the protonolysis of (COD)PtII(CH\u2083)\u2082 gave Arrhenius parameters outside semi-classical limits. On the other hand, protonolysis of (tmeda)PtII(CH\u2083)Cl (tmeda = N,N,N\u2019,N\u2019\u2013tetramethyl\u2013ethylenediamine) by trifluoroacetic acid gave normal kinetic isotope effects and classical Arrhenius parameters. Density functional theory (DFT) was used to examine the mechanism of protonolysis of these two systems, and the results were found to be consistent with experimental observations. Based on our experimental and computational work, we propose that protonolysis of methylplatinium(II) complexes can occur through either a concerted or stepwise pathway that is highly ligand dependent; more electron-rich ligands will favor the stepwise mechanism, while electron-deficient ligands with stronger trans influence will favor the concerted mechanism. Finally, we propose that the presence of abnormally large KIEs is an indication for a concerted pathway, and that there is a connection between the magnitude and temperature dependence of the KIE and mechanism.
\r\n\r\nIn aqueous solution, [PtII(glycinato)Cl\u2082]\u207b catalyzes oxidation by [PtIVCl\u2086]\u00b2\u207b of the methyl group of p-toluenesulfonate to the corresponding alcohol and aldehyde, with no further oxidation to the carboxylic acid. Both rate and selectivity are improved in comparison to the original Shilov system that employs [PtIICln(H\u2082O)4-n]2-n as the catalyst.
\r\n", "date": "2010", "date_type": "degree", "id_number": "CaltechTHESIS:12012009-210811032", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:12012009-210811032", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "deposited_by": "George Chen", "deposited_on": "2009-12-23 16:53:33", "doi": "10.7907/G7TZ-QS84", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" }, { "email": "jal@its.caltech.edu", "id": "Labinger-J-A", "name": { "family": "Labinger", "given": "Jay A." }, "role": "co-advisor" } ] }, "thesis_committee": { "items": [ { "email": "jal@its.caltech.edu", "id": "Labinger-J-A", "name": { "family": "Labinger", "given": "Jay A." }, "role": "chair" }, { "email": "tirrell@caltech.edu", "id": "Tirrell-D-A", "name": { "family": "Tirrell", "given": "David A." }, "role": "member" }, { "email": "nslewis@its.caltech.edu", "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan Saul" }, "role": "member" }, { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "member" }, { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "2009-11-16", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "2010", "author_list": "Chen, George Shuxiong", "advisor_list": "Bercaw, John E. and Labinger, Jay A.", "comittee_list": "Labinger, Jay A.; Tirrell, David A.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/5925", "eprint_id": 5925, "rev_number": 21, "documents": [ { "id": "/id/document/10435", "doc_id": 10435, "rev_number": 5, "files": [ { "id": "/id/file/72053", "fileid": 72053, "datasetid": "document", "objectid": 10435, "filename": "Thesis_SRG.pdf", "mime_type": "application/pdf", "filesize": 8246412, "mtime": "2012-12-26 04:28:49", "url": "/5925/1/Thesis_SRG.pdf" } ], "eprint_id": 5925, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": "Thesis_SRG.pdf", "media_duration": "0", "media_aspect_ratio": "0", 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"/id/document/10435" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/10435" } ] } } ], "eprint_status": "archive", "userid": 1848, "dir": "disk0/00/00/59/25", "datestamp": "2010-06-08 15:57:02", "lastmod": "2019-11-08 18:11:44", "status_changed": "2010-06-08 15:57:02", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "sgolisz@gmail.com", "id": "Golisz-Suzanne-Rose", "name": { "family": "Golisz", "given": "Suzanne Rose" }, "show_email": "NO" } ] }, "title": "Organometallic Reaction Mechanisms: Olefin Polymerization Catalysis and C-H Bond Activation by Early Transition Metal Bisphenolate Complexes and Protonolysis of Bipyrimidine Platinum Methyl Complexes ", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "Mechanistic aspects of organometallic transformations such as polymerization, C H activation, and protonolysis have been examined. Relationships between catalyst geometry and polymer microstructure were defined. The mechanism of an intramolecular C H activation process was found to involve two competing pathways. The protonolysis of platinum methyl complexes was investigated for kinetic isotope effects and observation of intermediates.
\r\n\r\nBisphenolate ligands with pyridine and benzene diyl linkers were synthesized and metalated with group 4 and 5 transition metals. The solid state structures of some of the group 4 complexes were solved. The titanium, zirconium, hafnium, and vanadium complexes were tested for propylene, 1 hexene, and ethylene/1 octene polymerization activities with methylaluminoxane as co catalyst. Titanium and zirconium (IV) precatalysts with pyridine diyl linkers provided mixtures of isotactic and atactic polypropylene while titanium (IV) precatalysts with benzene diyl linkers gave atactic polypropylene only. The hafnium (IV) precatalyst with a pyridine diyl linker generated moderately isotactic polypropylene.
\r\n\r\nA titanium dibenzyl complex featuring a ligand with two phenolates linked by a benzene diyl was found to undergo thermal decomposition to give toluene and a cyclometalated dimeric complex. The thermal decomposition followed first order kinetics and was studied at a number of temperatures to determine the activation parameters. Deuterated isotopologs were synthesized to measure the kinetic isotope effects. The complexes with deuterium in the benzyl methylene positions decomposed slower than the protio analogs. Isotopologs of toluene with multiple deuteration positions were observed in the product mixtures. These data are consistent with competing \u03b1-abstraction and \u03c3-bond metathesis.
\r\n \r\nThe protonolysis of bipyrimidine ligated platinum (II) complexes was explored. The bipyrimidine platinum dimethyl complex (bpm)PtMe\u2082 was shown to undergo protonation at the metal upon addition of trifluoroacetic acid (tfa) to give a platinum (IV) hydride intermediate which reductively eliminated methane to give (bpm)PtMe(tfa). Using a mixture of deutero and protio acid, all isotopologs of methane were observed. The protonation of (bpm)PtMe(tfa) was less straightforward as no intermediates were found, and CH\u2084, CH\u2083D, and CH\u2082D\u2082 were observed upon addition of a mixture of deutero and protio acid. The protonation of a nitrogen of the bpm ligand was also examined and determined improbable under the present conditions.
\r\n", "date": "2010", "date_type": "degree", "id_number": "CaltechTHESIS:06072010-114755605", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:06072010-114755605", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Gayle Hammer", "deposited_by": "Suzanne Golisz", "deposited_on": "2010-06-08 15:57:02", "doi": "10.7907/BBBN-SA63", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" }, { "email": "jal@its.caltech.edu", "id": "Labinger-J-A", "name": { "family": "Labinger", "given": "Jay A." }, "role": "co-advisor" } ] }, "thesis_committee": { "items": [ { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "chair" }, { "email": "tirrell@caltech.edu", "id": "Tirrell-D-A", "name": { "family": "Tirrell", "given": "David A." }, "role": "member" }, { "email": "stoltz@caltech.edu", "id": "Stoltz-B-M", "name": { "family": "Stoltz", "given": "Brian M." }, "role": "member" }, { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" }, { "email": "jal@its.caltech.edu", "id": "Labinger-J-A", "name": { "family": "Labinger", "given": "Jay A." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "2010-05-24", "gradofc_approval_date": "2010-06-07", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "2010", "author_list": "Golisz, Suzanne Rose", "advisor_list": "Bercaw, John E. and Labinger, Jay A.", "comittee_list": "Gray, Harry B.; Tirrell, David A.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/1255", "eprint_id": 1255, "rev_number": 12, "documents": [ { "id": "/id/document/1901", "doc_id": 1901, "rev_number": 2, "files": [ { "id": "/id/file/11920", "fileid": 11920, "datasetid": "document", "objectid": 1901, "filename": "bolin_thesis_final.pdf", "mime_type": "application/pdf", "filesize": 6046031, "mtime": "2012-12-26 02:36:41", "url": "/1255/1/bolin_thesis_final.pdf" } ], "eprint_id": 1255, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "format_desc": "bolin_thesis_final.pdf", "language": "en", "security": "public", "license": "other", "main": "bolin_thesis_final.pdf", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "final", "relation": { "items": [ { "type": "http://eprints.org/relation/hasVolatileVersion", "uri": "/id/document/18680" }, { "type": "http://eprints.org/relation/haspreviewThumbnailVersion", "uri": "/id/document/18680" }, { "type": "http://eprints.org/relation/hasVersion", "uri": "/id/document/18680" } ] } }, { "id": "/id/document/18680", "doc_id": 18680, "rev_number": 2, "files": [ { "id": "/id/file/11918", "fileid": 11918, "datasetid": "document", "objectid": 18680, "filename": "preview.png", "mime_type": "image/png", "hash": "e2274cfbb63115526069fe69719b9737", "hash_type": "MD5", "filesize": 8717, "mtime": "2012-12-26 02:36:41", "url": "/1255/2/preview.png" } ], "eprint_id": 1255, "pos": 2, "placement": 2, "mime_type": "image/png", "format": "image/png", "language": "en", "security": "public", "license": "other", "main": "preview.png", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/1901" }, { "type": "http://eprints.org/relation/ispreviewThumbnailVersionOf", "uri": "/id/document/1901" }, { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/1901" } ] } }, { "id": "/id/document/120603", "doc_id": 120603, "rev_number": 1, "files": [ { "id": "/id/file/365991", "fileid": 365991, "datasetid": "document", "objectid": 120603, "filename": "indexcodes.txt", "mime_type": "text/plain", "hash": "dea8e391edd232cbdd8fc30761c4f1c1", "hash_type": "MD5", "filesize": 27681, "mtime": "2021-06-23 20:56:54", "url": "/1255/3/indexcodes.txt" } ], "eprint_id": 1255, "pos": 3, "placement": 3, "mime_type": "text/plain", "format": "other", "format_desc": "Generate index codes conversion from application/pdf to indexcodes", "language": "en", "security": "public", "license": "other", "main": "indexcodes.txt", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/1901" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/1901" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/1901" } ] } } ], "eprint_status": "archive", "userid": 2, "dir": "disk0/00/00/12/55", "datestamp": "2009-06-01", "lastmod": "2019-11-26 20:36:45", "status_changed": "2009-09-25 01:59:37", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "bolin.lin@gmail.com", "id": "Lin-Bo-Lin", "name": { "family": "Lin", "given": "Bo-Lin" }, "show_email": "NO" } ] }, "title": "A Combined Experimental and Computational Study of Ligand Effects on C-H Bond Activation by Palladium and Platinum Complexes", "ispublished": "unpub", "full_text_status": "public", "keywords": "hydrocarbon oxidation", "abstract": "Abnormally large kinetic hydrogen/deuterium isotope effects (KIEs, ~ 20) are measured for the protonolysis of several dimethylpalladium(II) complexes with various bidentate ligands by trifluoroethanol (TFE) at room temperature. Analyses of semiclassical KIE theory suggest that the occurrence of hydrogen tunneling needs to be invoked in order to explain these KIE values, which is further supported by the KIE-temperature-dependence study for the protonolysis of (dppe)Pd(CH\u2083)\u2082 by CF\u2083CD\u2082OD/CF\u2083CH\u2082OH.
\r\n\r\nDensity functional theory (DFT) computation suggests that protonation at the MII-C bond is kinetically preferred over protonation at the metal center for the protonolysis of (COD)Pt(CH\u2083)\u2082 by TFA and the dimethylpalladium(II) complexes by TFE in dichloroethane. The computation further indicates the significant contribution of hydrogen tunneling in the abnormally large KIEs observed experimentally.
\r\n\r\nThe monomethylpalladium(II) complex, (COD)Pd(CH\u2083)Cl (COD = 1,5-cyclooctadiene), undergoes both benzene C-H activation and migratory insertion of olefin, with the former faster than the latter, at room temperature under the assistance of an anionic \u03b2-diketiminate ligand, to yield \u03b7\u00b3-(2-R-cyclooctenyl)palladium(II) \u03b2-diketiminate (R = methyl or phenyl).
\r\n\r\nDFT computation result suggests that bisindolide-type ligands and carbenearyl-type ligands are likely to lead to faster benzene C-H bond activation as well as lower relative VIII barrier heights of the C-H bond activation versus the insertion of olefins than those in monomethyl palladium(II) with \u03b2-diketiminate.
\r\n\r\nSeveral pyridine-like ligands were found to improve Pd(OAc)\u2082-catalyzed allylic oxidation of allylbenzene to cinnamyl acetate by p-benzoquinone in acetic acid. The best ligand examined, bipyrimidine, was used to identify the catalyst precursor for this system, (bipyrimidine)Pd(OAc)\u2082, which was fully characterized. Mechanistic studies suggest the reaction takes place through disproportionation of (bipyrimidine)Pd(OAc)\u2082 to form a bipyrimidine-bridged dimer, which reacts with olefin to form a PdII-olefin adduct, followed by allylic C-H activation to produce (\u03b7\u00b3-allyl)PdII species. The (\u03b7\u00b3-allyl)PdII intermediate undergoes a reversible acetate attack to generate a Pd\u2070-(allyl acetate) adduct, which subsequently reacts with p-benzoquinone to release allyl acetate and regenerate (bipyrimidine)Pd(OAc)\u2082. No KIE is observed for the competition experiment between allylbenzene-d\u2080 and allylbenzene-d\u2085(CD\u2082=CD-CD\u2082-C\u2086H\u2085), suggesting that allylic C-H activation is not rate determining. Catalytic allylic acetoxylations of other terminal olefins as well as cyclohexene were also effected by (bipyrimidine)Pd(OAc)\u2082.
\r\n", "date": "2009", "date_type": "degree", "id_number": "CaltechETD:etd-04022009-144521", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechETD:etd-04022009-144521", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "suggestions": "archival copy - 35047019439918", "deposited_by": "Imported from ETD-db", "deposited_on": "2009-06-01", "doi": "10.7907/PD2Z-QZ56", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "rhg@caltech.edu", "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "role": "chair" }, { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" }, { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "member" }, { "email": "lhw@caltech.edu", "id": "Hsieh-Wilson-L-C", "name": { "family": "Hsieh-Wilson", "given": "Linda C." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_submitted_date": "2009-04-02", "thesis_defense_date": "2009-03-18", "thesis_approved_date": "2009-06-01", "gradofc_approval_date": "2009-05-29", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive\nlicense to archive and make accessible, under the conditions specified below,\nmy thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "2009", "author_list": "Lin, Bo-Lin", "advisor_list": "Bercaw, John E.", "comittee_list": "Grubbs, Robert H.; Bercaw, John E.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/5176", "eprint_id": 5176, "rev_number": 16, "documents": [ { "id": "/id/document/8187", "doc_id": 8187, "rev_number": 3, "files": [ { "id": "/id/file/50461", "fileid": 50461, "datasetid": "document", "objectid": 8187, "filename": "drw_Thesis.pdf", "mime_type": "application/pdf", "filesize": 16833331, "mtime": "2012-12-26 03:15:34", "url": "/5176/1/drw_Thesis.pdf" } ], "eprint_id": 5176, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "format_desc": "drw_Thesis.pdf", "language": "en", "security": "public", "license": "other", "main": "drw_Thesis.pdf", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "final", "relation": { "items": [ { "type": "http://eprints.org/relation/hasVolatileVersion", "uri": "/id/document/24690" }, { "type": "http://eprints.org/relation/haspreviewThumbnailVersion", "uri": "/id/document/24690" }, { "type": "http://eprints.org/relation/hasVersion", "uri": "/id/document/24690" } ] } }, { "id": "/id/document/13775", "doc_id": 13775, "rev_number": 3, "files": [ { "id": "/id/file/204542", "fileid": 204542, "datasetid": "document", "objectid": 13775, "filename": "Weinberg_release_request_nov2011.txt", "mime_type": "text/plain", "filesize": 1336, "mtime": "2016-08-22 21:17:49", "url": "/5176/2/Weinberg_release_request_nov2011.txt" } ], "eprint_id": 5176, "pos": 2, "format": "text/plain", "format_desc": "release request nov2011", "language": "en", "security": "internal", "license": "other", "main": "Weinberg_release_request_nov2011.txt", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "release" }, { "id": "/id/document/24690", "doc_id": 24690, "rev_number": 2, "files": [ { "id": "/id/file/50459", "fileid": 50459, "datasetid": "document", "objectid": 24690, "filename": "preview.png", "mime_type": "image/png", "hash": "bf0a906897d8594e073d0fcff1f38904", "hash_type": "MD5", "filesize": 8804, "mtime": "2012-12-26 03:15:34", "url": "/5176/3/preview.png" } ], "eprint_id": 5176, "pos": 3, "placement": 3, "mime_type": "image/png", "format": "image/png", "language": "en", "security": "public", "license": "other", "main": "preview.png", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/8187" }, { "type": "http://eprints.org/relation/ispreviewThumbnailVersionOf", "uri": "/id/document/8187" }, { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/8187" } ] } }, { "id": "/id/document/124862", "doc_id": 124862, "rev_number": 1, "files": [ { "id": "/id/file/370292", "fileid": 370292, "datasetid": "document", "objectid": 124862, "filename": "indexcodes.txt", "mime_type": "text/plain", "hash": "09ef69c8c7bbe3ccc47ca5b7b4a04636", "hash_type": "MD5", "filesize": 37664, "mtime": "2021-06-23 23:56:58", "url": "/5176/4/indexcodes.txt" } ], "eprint_id": 5176, "pos": 4, "placement": 4, "mime_type": "text/plain", "format": "other", "format_desc": "Generate index codes conversion from application/pdf to indexcodes", "language": "en", "security": "public", "license": "other", "main": "indexcodes.txt", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/8187" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/8187" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/8187" } ] } }, { "id": "/id/document/124863", "doc_id": 124863, "rev_number": 1, "files": [ { "id": "/id/file/370293", "fileid": 370293, "datasetid": "document", "objectid": 124863, "filename": "indexcodes.txt", "mime_type": "text/plain", "hash": "9655958003ed4a7a83d12f12c79865df", "hash_type": "MD5", "filesize": 779, "mtime": "2021-06-23 23:56:58", "url": "/5176/5/indexcodes.txt" } ], "eprint_id": 5176, "pos": 5, "placement": 5, "mime_type": "text/plain", "format": "other", "format_desc": "Generate index codes conversion from text/plain to indexcodes", "language": "en", "security": "internal", "license": "other", "main": "indexcodes.txt", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/13775" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/13775" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/13775" } ] } } ], "eprint_status": "archive", "userid": 2, "dir": "disk0/00/00/51/76", "datestamp": "2009-05-29", "lastmod": "2019-11-26 20:38:07", "status_changed": "2012-01-10 19:11:42", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "davidrweinberg@gmail.com", "id": "Weinberg-David-Richard", "name": { "family": "Weinberg", "given": "David Richard" }, "show_email": "YES" } ] }, "title": "Investigations into the Requirements for Homogeneous Platinum- and Iridium-Catalyzed Oxidative C-H Bond Functionalization\r ", "ispublished": "unpub", "full_text_status": "public", "keywords": "carbene; dianionic ligand; dianionic platinum complex; diphenolate; imidazolyl; iridium dimer; phosphoraniminate", "abstract": "Investigations have been performed to determine the requirements for homogeneous platinum- and iridium-catalyzed oxidative alkane functionalization. Previous platinum-catalyzed systems have involved initial C-H bond activation to generate a platinum(II)-alkyl, followed by two-electron oxidation of this species to activate the alkyl towards nucleophilic displacement from the metal center. The factors affecting C-H bond activation by platinum(II) complexes and oxidation of alkylplatinum(II) complexes have been probed, while the possibility of using a diphenolate imidazolyl-carbene ligand to stabilize iridium complexes in a variety of oxidation states has been explored.
\r\n\r\nRelative oxidation and protonation rates for trichloro(methyl)platinum(II) dianion have been screened under a variety of conditions, using several different oxidants. Both one- and two-electron oxidants were shown to compete effectively with protonation of trichloro(methyl)platinum(II) dianion, including CuCl2, CuBr2, FeCl3, Na3[H3PMo9V3O40], Br2, Na2IrCl6, and (NH4)2Ce(NO3)6. Oxidation by copper(II) proved to be highly dependent on the counteranion.
\r\n\r\nDisodium (2,2\u2019-biindolyl)dimethylplatinum(II) has been synthesized for the purpose of probing the C-H bond activation chemistry of electron rich platinum(II) complexes. This complex decomposes rapidly in air, and deuterolysis of both platinum-methyls as well as the 2,2\u2019-biindolyl ligand occurs when it is dissolved in methanol-d4. Methide abstraction from (2,2\u2019-biindolyl)dimethylplatinum(II), either by protonolysis or by reaction with B(C6F5)3, generates monomethylplatinum(II) species capable of activating C-H and C-D bonds.
\r\n\r\nIn the search for ligands capable of stabilizing iridium complexes in a variety of oxidation states, the first iridium complexes containing a diphenolate imidazolyl-carbene ligand have been synthesized. 1,3-Di(2-hydroxy-5-tert-butylphenyl)imidazolium chloride was synthesized and then reacted with chloro-1,5-cyclooctadiene iridium(I) dimer to generate potassium (1,5-cyclooctadiene){1,3-di(2-hydroxy-5-tert-butylphenyl)imidazolyl}iridium(I). Oxidation of this complex with two equivalents of ferrocenium(III) hexafluorophosphate generates (acetonitrile)(1,5-cyclooctadiene){1,3-di(2-hydroxy-5-tert-butylphenyl)imidazolyl}iridium(III) hexafluorophosphate. Reaction of this complex with dihydrogen generates a species capable of catalyzing olefin hydrogenations. Heating (acetonitrile)(1,5-cyclooctadiene){1,3-di(2-hydroxy-5-tert-butylphenyl)imidazolyl}iridium(III) hexafluorophosphate with greater than two equivalents of tricyclohexylphosphine in acetonitrile followed by treatment with tetramethylammonium chloride results in (chloro)bis(tricyclohexylphosphine){1,3-di(2-hydroxy-5-tert-butylphenyl)imidazolyl}iridium(III). As indicated by cyclic voltammetry and bulk electrolysis, this complex undergoes two reversible one-electron oxidations in methylene chloride at -0.22 V and at 0.58 V.
\r\n", "date": "2009", "date_type": "degree", "id_number": "CaltechETD:etd-02042009-144339", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechETD:etd-02042009-144339", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "deposited_by": "Imported from ETD-db", "deposited_on": "2009-05-29", "doi": "10.7907/TAYG-C375", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "rhg@caltech.edu", "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "role": "chair" }, { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "member" }, { "email": "jal@its.caltech.edu", "id": "Labinger-J-A", "name": { "family": "Labinger", "given": "Jay A." }, "role": "member" }, { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" }, { "email": "nslewis@caltech.edu", "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan Saul" }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_submitted_date": "2009-02-04", "thesis_defense_date": "2008-11-26", "thesis_approved_date": "2009-05-29", "gradofc_approval_date": "2009-04-24", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. 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"other", "format_desc": "Generate index codes conversion from text/plain to indexcodes", "language": "en", "security": "internal", "license": "other", "main": "indexcodes.txt", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/13689" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/13689" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/13689" } ] } } ], "eprint_status": "archive", "userid": 2, "dir": "disk0/00/00/52/40", "datestamp": "2008-07-31", "lastmod": "2019-11-26 20:38:13", "status_changed": "2011-10-05 16:24:18", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "elowe@caltech.edu", "id": "Elowe-Paul-Richard", "name": { "family": "Elowe", "given": "Paul Richard" }, "show_email": "NO" } ] }, "title": "The Selective Oligomerization of Ethylene Using Chromium Diphosphine Catalysts and the Synthesis and Reactivity of Group 7 Carbonyl Derivatives Relevant to Synthesis Gas Conversion", "ispublished": "unpub", "full_text_status": "public", "keywords": "C-C bond formation; carbonyl complexes; catalysis; chemistry; ethylene; oligomerization; organometallic chemistry; synthesis gas", "abstract": "The work presented in this thesis explores two distinct fields of organometallic chemistry with a common goal of selectively transforming cheap and abundant feedstocks to value-added chemicals using homogeneous catalysts.
\r\n\r\nChapter 1 presents the synthesis and characterization of a series of bis(diphenylphosphino)amine ligands and their corresponding chromium(III) trichloride complexes. The isolated chromium complexes are precursors to highly active catalysts for the selective oligomerization of ethylene to 1-hexene and 1-octene. The unique feature of the ligands presented herein is the presence of coordinating functionalities tethered to the nitrogen backbone. These act as hemilabile donors, which stabilize the active species and/or transition states during catalysis. This increased stability leads to more productive catalysts. Furthermore, important solvent and additive effects have been investigated. While reactions in non-polar solvents exhibit poor activity at lower ethylene pressures, those in more polar solvents are highly active and generate very little undesired polymer. Varying the solvent has a significant impact on 1-hexene/1-octene selectivity as well. Experiments with potentially coordinating additives result in a higher tendency for 1-octene formation. An investigation of catalyst decomposition is also discussed.
\r\n\r\nChapter 2 presents synthetic, structural and reactivity studies on a series of Group 7 carbonyl derivatives relevant to synthesis gas conversion. Reduction of the carbonyl precursors with a hydride source generates the corresponding formyl species. This reaction is facilitated when more electrophilic carbonyl complexes are employed. Neutral and cationic Fischer carbene complexes were prepared by the reaction of the formyl species with boranes and alkyltriflates, respectively. Further reduction of Group 7 methoxycarbenes with a hydride leads to the formation of a reactive methoxymethyl species. Dimethyl ether release is obtained from treatment of a manganese methoxymethyl species with a hydride. Moreover, subjecting manganese methoxymethyl complexes to an atmosphere of CO generates acyl complexes via migratory insertion. Preliminary mechanistic details are presented.
\r\n", "date": "2009", "date_type": "degree", "id_number": "CaltechETD:etd-07252008-141614", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechETD:etd-07252008-141614", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "suggestions": "prelowe@dow.com", "deposited_by": "Imported from ETD-db", "deposited_on": "2008-07-31", "doi": "10.7907/S7NA-Y054", "alt_title": { "items": [ "Synthesis and Reactivity of Group 7 Carbonyl Derivatives Relevant to Synthesis Gas Conversion" ] }, "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "chair" }, { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "co-chair" }, { "email": "datirrell@caltech.edu", "id": "Tirrell-D-A", "name": { "family": "Tirrell", "given": "David A." }, "role": "member" }, { "email": "jkbarton@caltech.edu", "id": "Barton-J-K", "name": { "family": "Barton", "given": "Jacqueline K." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_submitted_date": "2008-07-25", "thesis_defense_date": "2008-07-17", "thesis_approved_date": "2008-07-31", "gradofc_approval_date": "2008-07-29", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive\nlicense to archive and make accessible, under the conditions specified below,\nmy thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "2009", "author_list": "Elowe, Paul Richard", "advisor_list": "Bercaw, John E.", "comittee_list": "Bercaw, John E.; Gray, Harry B.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/5181", "eprint_id": 5181, "rev_number": 20, "documents": [ { "id": "/id/document/8192", "doc_id": 8192, "rev_number": 4, "files": [ { "id": "/id/file/50537", "fileid": 50537, "datasetid": "document", "objectid": 8192, "filename": "Thesis.pdf", "mime_type": "application/pdf", "filesize": 21767866, "mtime": "2012-12-26 03:15:37", "url": "/5181/1/Thesis.pdf" } ], "eprint_id": 5181, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": "Thesis.pdf", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", 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} } ], "eprint_status": "archive", "userid": 2, "dir": "disk0/00/00/51/81", "datestamp": "2007-04-19", "lastmod": "2020-02-26 23:41:57", "status_changed": "2009-10-07 18:40:03", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "agapie@caltech.edu", "id": "Agapie-Theodor", "name": { "family": "Agapie", "given": "Theodor" }, "orcid": "0000-0002-9692-7614", "show_email": "NO" } ] }, "title": "Synthetic, Reactivity, and Mechanistic Studies Relevant to Olefin Oligomerization and Polymerization", "ispublished": "unpub", "full_text_status": "public", "keywords": "alkylidene; CH bond activation; ethylene trimerization; fluxional process; nonmetallocene catalysts; olefin polymerization", "abstract": "Chapters 2 and 3 present synthetic, structural, and mechanistic studies relevant to the selective trimerization of ethylene to 1-hexene using a chromium diphosphine catalyst system. The studied diphosphines, PNPL=(o-L-C\u2086H\u2084)\u2082PN(Me)P(o-L-C\u2086H\u2084)\u2082, display a PNP backbone with phosphine-aryl groups ortho-substituted with ethers, amines, or thioethers (L=OMe, NMe2, or SMe). Chromium(0) and chromium(III) complexes have been prepared, characterized structurally, and tested for catalytic activity, highlighting the importance of the pendant ether groups. A chromacyclopentane model complex, (PNPO4)Cr(o,o-biphenyldiyl)Br, has been isolated using the parent phosphine system (PNPO4, L=OMe). Starting with this model system, the olefin trimerization reaction has been investigated using trans-, cis-, and gem-d2-ethylene as well as mixtures of C\u2082D\u2084 and C\u2082H\u2084. The selectivity of \u03b1-olefin insertion into the chromacyclopentane mimic and that of \u03b2-H elimination from chromacycloheptanes have been studied. The relative rates of insertion of terminal and internal olefins into the chromacyclopentane moiety have been measured.
\r\n\r\nChapters 4, 5, and 6 present synthetic studies of tantalum, titanium, and zirconium complexes supported by a new tridentate bisphenolate framework, along with applications to olefin polymerization and mechanistic studies of organometallic transformations based on these architectures. The utilized ligand framework involves a bisphenol connected at the ortho positions via semirigid, ring-ring (sp\u00b2-sp\u00b2) linkages to a flat ring (pyridine, thiophene, furan, or benzene). These ligands were found to coordinate to metals in a mer fashion to give a variety of binding geometries. A tantalum system supported by the benzene bridged bisphenolate was found to undergo intramolecular CH activation faster than metal-alkyl protonolysis by a pendant phenol, un unprecedented process for early metals. An \u03b1-H abstraction reaction has afforded access to a tantalum benzylidene supported by the pyridine linked bisphenolate. Isotope labeling studies and variable temperature kinetics measurements were used to investigate the mechanisms of these transformations. Group 4 complexes supported by the present bisphenolates were found to have interesting catalytic behavior for the propylene polymerization and oligomerization, upon activation with excess MAO. The propylene polymerization activity of present zirconium complexes is excellent, exceeding 10\u2076 g polypropylene / (mol Zr \u2022 h), in some cases.
\r\n\r\nChapter 7 presents the synthesis and study of group 3 dialkyl complexes supported by tetradentate L2N-phenolates (L = S, N, O). These complexes were found to undergo a non-dissociative ligand exchange process in solution. The mechanism of this process was studied by using variable temperature NMR spectroscopy.
", "date": "2007", "date_type": "degree", "id_number": "CaltechETD:etd-04092007-132543", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechETD:etd-04092007-132543", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "deposited_by": "Imported from ETD-db", "deposited_on": "2007-04-19", "doi": "10.7907/R42C-K778", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "rhb@caltech.edu", "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "role": "chair" }, { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "member" }, { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" }, { "email": "jpeters@caltech.edu", "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_submitted_date": "2007-04-09", "thesis_defense_date": "2007-01-22", "thesis_approved_date": "2007-04-19", "gradofc_approval_date": "2007-04-19", "thesis_awards": "The Herbert Newby McCoy Award, 2007.", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive\nlicense to archive and make accessible, under the conditions specified below,\nmy thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "2007", "author_list": "Agapie, Theodor", "advisor_list": "Bercaw, John E.", "comittee_list": "Grubbs, Robert H.; Gray, Harry B.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/1839", "eprint_id": 1839, "rev_number": 9, "documents": [ { "id": "/id/document/3064", "doc_id": 3064, "rev_number": 3, "files": [ { "id": "/id/file/18453", "fileid": 18453, "datasetid": "document", "objectid": 3064, "filename": "JABthesisJEB053.pdf", "mime_type": "application/pdf", "filesize": 28790779, "mtime": "2012-12-26 02:42:54", "url": "/1839/1/JABthesisJEB053.pdf" } ], "eprint_id": 1839, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "format_desc": "Full thesis", "language": "en", "security": "public", "license": "other", "main": "JABthesisJEB053.pdf", "media_duration": "0", 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1839, "pos": 8, "placement": 8, "mime_type": "text/x-c", "format": "other", "format_desc": "Generate index codes conversion from application/pdf to indexcodes", "language": "en", "security": "public", "license": "other", "main": "indexcodes.txt", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/3064" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/3064" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/3064" } ] } } ], "eprint_status": "archive", "userid": 2, "dir": "disk0/00/00/18/39", "datestamp": "2007-05-31", "lastmod": "2020-02-28 22:46:37", "status_changed": "2009-09-25 02:17:15", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "jabyers@caltech.edu", "id": "Byers-Jeffery-Allen", "name": { "family": "Byers", "given": "Jeffery Allen" }, "orcid": "0000-0002-8109-674X", "show_email": "NO" } ] }, "title": "Synthetic and Mechanistic Studies into the Kinetic Resolution of \u03b1-olefins Using C\u2081\u208b and C\u2082\u208b Symmetric Zirconocene Polymerization Catalysts", "ispublished": "unpub", "full_text_status": "public", "keywords": "13C labeled olefin; asymmetric catalysis; swivel frit", "abstract": "Mechanistic and synthetic investigations into the kinetic resolution of racemic \u03b1-olefins by polymerization catalysis using C\u2081\u208b and C\u2082\u208bsymmetric zirconocenes are reported. The importance of chain end control as a stereocontrol element was probed with ethylene and propylene copolymerizations catalyzed by the C\u2081\u208bsymmetric catalyst, {1,2-(SiMe\u2082)\u2082(\u03b7\u2075-3,5-C\u2085H\u2081(CHMe\u2082)\u2082)(\u03b7\u2075-4-C\u2085H\u2082((S)-CHMeCMe\u2083)]}ZrCl\u2082/MAO. Selectivity factors and pentad analysis of racemic \u03b1-olefin and propylene polymerizations catalyzed by a similar C\u2081\u208bsymmetric catalyst, {1,2-(SiMe\u2082)\u2082(\u03b7\u2075-3,5-C\u2085H\u2081(CHMe\u2082)\u2082)(\u03b7\u2075-4-C\u2085H\u2082((S)-CHEtCMe\u2083)]}ZrCl\u2082/MAO, indicate that site epimerization does not limit selectivity during kinetic resolution.
\r\n\r\nTo avoid some of the issues involved with the C\u2081\u208bsymmetric catalysts, a route to enantiopure C\u2082\u208bsymmetric zirconocenes was pursued. With the aid of the chiral auxiliary, (R)-N2,N2\u2019-di-p-tolyl-1,1\u2019-binaphtyl-2,2\u2019-diamine, enantiospecefic synthesis of (S,S)-{C\u2082H\u2084 -1,2-(1-indene)\u2082}ZrCl\u2082 was accomplished and its use for kinetic resolution was investigated. Although synthetically useful selectivities were not observed, it was determined that the C\u2082\u208bsymmetric catalyst does not racemize during polymerization, which substantiates a more thorough investigation of catalysts based on {C\u2082H\u2084 -1,2-(1-indene)\u2082}ZrCl\u2082.
", "date": "2007", "date_type": "degree", "id_number": "CaltechETD:etd-05162007-152948", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechETD:etd-05162007-152948", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "deposited_by": "Imported from ETD-db", "deposited_on": "2007-05-31", "doi": "10.7907/H55G-7C87", "alt_title": { "items": [ "Synthetic and mechanistic studies into the kinetic resolution of alpha-olefins using C1- and C2- symmetric zirconocene polymerization catalysts" ] }, "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." } } ] }, "thesis_committee": { "items": [ { "email": "stoltz@caltech.edu", "id": "Stoltz-B-M", "name": { "family": "Stoltz", "given": "Brian M." }, "role": "chair" }, { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" }, { "email": "jpeters@caltech.edu", "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "role": "member" }, { "email": "rhg@caltech.edu", "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_submitted_date": "2007-05-16", "thesis_defense_date": "2007-05-24", "thesis_approved_date": "2007-05-31", "gradofc_approval_date": "2007-05-31", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive\nlicense to archive and make accessible, under the conditions specified below,\nmy thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "2007", "author_list": "Byers, Jeffery Allen", "advisor_list": "Bercaw, John E.", "comittee_list": "Stoltz, Brian M.; Bercaw, John E.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/4588", "eprint_id": 4588, "rev_number": 9, "documents": [ { "id": "/id/document/7422", "doc_id": 7422, "rev_number": 3, "files": [ { "id": "/id/file/45351", "fileid": 45351, "datasetid": "document", "objectid": 7422, "filename": "SSThesis.pdf", "mime_type": "application/pdf", "filesize": 8673088, "mtime": "2012-12-26 03:10:01", "url": "/4588/1/SSThesis.pdf" } ], "eprint_id": 4588, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": "SSThesis.pdf", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "final", "relation": { "items": [ { "type": "http://eprints.org/relation/hasVolatileVersion", "uri": "/id/document/23947" }, { "type": "http://eprints.org/relation/haspreviewThumbnailVersion", "uri": "/id/document/23947" }, { "type": "http://eprints.org/relation/hasVersion", "uri": "/id/document/23947" } ] } }, { "id": "/id/document/16268", "doc_id": 16268, "rev_number": 3, "files": [ { "id": "/id/file/204392", "fileid": 204392, "datasetid": "document", "objectid": 16268, "filename": "Min_Endy_Yeo-Jung_2006.PDF", "mime_type": "application/pdf", "filesize": 40103, "mtime": "2016-08-22 21:17:28", "url": "/4588/2/Min_Endy_Yeo-Jung_2006.PDF" } ], "eprint_id": 4588, "pos": 2, "format": "application/pdf", "language": "en", "security": "internal", "license": "other", "main": "Min_Endy_Yeo-Jung_2006.PDF", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "approvalform" }, { "id": "/id/document/23947", "doc_id": 23947, "rev_number": 2, "files": [ { "id": "/id/file/45349", "fileid": 45349, "datasetid": "document", "objectid": 23947, "filename": "preview.png", "mime_type": "image/png", "hash": "823fc1a6b88f378d50c5a4d9b0306ba2", "hash_type": "MD5", "filesize": 10092, "mtime": "2012-12-26 03:10:01", "url": "/4588/3/preview.png" } ], "eprint_id": 4588, "pos": 3, "placement": 3, "mime_type": "image/png", "format": "image/png", "language": "en", "security": "public", "license": "other", "main": "preview.png", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/7422" }, { "type": "http://eprints.org/relation/ispreviewThumbnailVersionOf", "uri": "/id/document/7422" }, { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/7422" } ] } }, { "id": "/id/document/124419", "doc_id": 124419, "rev_number": 1, "files": [ { "id": "/id/file/369849", "fileid": 369849, "datasetid": "document", "objectid": 124419, "filename": "indexcodes.txt", "mime_type": "text/plain", "hash": "3157db50f58aaaf2277c3b4377782559", "hash_type": "MD5", "filesize": 27642, "mtime": "2021-06-23 23:32:41", "url": "/4588/4/indexcodes.txt" } ], "eprint_id": 4588, "pos": 4, "placement": 4, "mime_type": "text/plain", "format": "other", "format_desc": "Generate index codes conversion from application/pdf to indexcodes", "language": "en", "security": "public", "license": "other", "main": "indexcodes.txt", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/7422" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/7422" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/7422" } ] } } ], "eprint_status": "archive", "userid": 2, "dir": "disk0/00/00/45/88", "datestamp": "2005-11-21", "lastmod": "2020-04-15 22:56:28", "status_changed": "2009-09-25 03:21:28", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Min-Endy-Yeo-Jung", "name": { "family": "Min", "given": "Endy Yeo-Jung" }, "show_email": "NO" } ] }, "title": "Kinetic Resolution of Chiral \u221d-Olefins Using Enantiopure Ziegler-Natta Polymerization Catalysts", "ispublished": "unpub", "full_text_status": "public", "keywords": "chiral olefin; kinetic resolution; polymerization; Ziegler-Natta catalyst", "abstract": "Towards the goal of kinetic resolution of chiral olefins, a series of enantiopure C1 symmetric metallocenes has been synthesized for use in the polymerization of chiral olefins. The new precatalysts were based on the parent precatalyst {(SiMe2)2[[eta]5-C5H(CHMe2)2][[eta]5-C5H2((S)-CHMeCMe3)]}ZrCl2, (S)-2, which has a doubly, silylene-linked ligand framework. The new precatalysts include {(SiMe2)2[[eta]5-C5H(CHEt2)2][[eta]5-C5H2((S)-CHMeCMe3)]}ZrCl2, (S)-3, {(SiMe2)2[[eta]5-C5H(CHCy2)2][[eta]5-C5H2((S)-CHMeCMe3)]}ZrCl2, (S)-4 (Cy = cyclohexyl), {(SiMe2)2[[eta]5-C5H(CHTMS2)2][[eta]5-C5H2((S)-CHMeCMe3)]}ZrCl2, (S)-5 (TMS = trimethylsilyl), and {(SiMe2)2[[eta]5-C5H(CHMe2)2][[eta]5-C5H2((S)-CHEtCMe3)]}ZrCl2, (S)-6.\r\n\r\nThe zirconocene dichlorides (S)-2, (S)-3, (S)-4, and (S)-5 have an enantiopure 3,3-dimethyl-2-butyl (\"methylneopentyl\") substituent on the \"upper\" cyclopentadienyl ligand. The zirconocene dichloride (S)-6 has an enantiopure 2,2-dimethyl-3-pentyl (\"ethylneopentyl\") substituent on the \"upper\" cyclopentadienyl ligand.\r\n\r\nWhen activated with methylaluminoxane (MAO), these metallocenes show unprecedented activity for the polymerization of racemic monomers bearing substitution at the 3- and/or 4-positions. In addition, due to the optically pure nature of these single site catalysts, polymerization of racemic monomers serves as a transition metal mediated kinetic resolution strategy. The polymeric product is enriched with the faster reacting enantiomer, while the recovered monomer is enriched with the slower reacting enantiomer. The two components are easily separated, thus affecting the resolution. A modest kinetic resolution was achieved (s = kfaster/kslower = ca. 2) with most olefins surveyed. In the case of 3,4-dimethyl-1-pentene and 3,4,4-trimethyl-1-pentene, high levels of separation were obtained (s > 12). X ray crystal structure determinations for (S)-2, (S)-3, and (S)-4 have been used to examine the prevailing steric interactions expected in the diastereomeric transition states for propagation during polymerization. In comparison to (S)-2, slight improvements in the selectivity of 3-methyl-1-hexene and 3,5,5-trimethyl-1-hexene were observed with polymerizations using (S)-3. Likewise, the polymerizations of 3-methyl-1-pentene and 3,5,5-trimethyl-1-hexene using (S)-6 showed a modest increase in selectivity, relative to (S)-2. The kinetic resolution of chiral olefins containing a polar functionality also has been attempted with (S)-2. Although the selectivity of these polymerization experiments is yet to be determined, preliminary work indicates that NMR can be used to analyze the (S)-Mosher esters of the olefins to obtain the enantiomeric excess.", "date": "2006", "date_type": "degree", "id_number": "CaltechETD:etd-11162005-125732", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechETD:etd-11162005-125732", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "deposited_by": "Imported from ETD-db", "deposited_on": "2005-11-21", "doi": "10.7907/ZD0X-9Y24", "alt_title": { "items": [ "Kinetic Resolution of Chiral alpha-Olefins Using Enantiopure Ziegler-Natta Polymerization Catalysts" ] }, "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "chair" }, { "email": "stoltz@caltech.edu", "id": "Stoltz-B-M", "name": { "family": "Stoltz", "given": "Brian M." }, "role": "member" }, { "email": "jak@cheme.caltech.edu", "id": "Kornfield-J-A", "name": { "family": "Kornfield", "given": "Julia A." }, "role": "member" }, { "email": "rhg@its.caltech.edu", "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_submitted_date": "2005-11-16", "thesis_defense_date": "2005-10-18", "thesis_approved_date": "2005-11-21", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive\nlicense to archive and make accessible, under the conditions specified below,\nmy thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "2006", "author_list": "Min, Endy Yeo-Jung", "advisor_list": "Bercaw, John E.", "comittee_list": "Bercaw, John E.; Stoltz, Brian M.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/2358", "eprint_id": 2358, "rev_number": 11, "documents": [ { "id": "/id/document/4484", "doc_id": 4484, "rev_number": 3, "files": [ { "id": "/id/file/25830", "fileid": 25830, "datasetid": "document", "objectid": 4484, "filename": "SBK-THESIS.pdf", "mime_type": "application/pdf", "filesize": 4372118, "mtime": "2012-12-26 02:50:33", "url": "/2358/1/SBK-THESIS.pdf" } ], "eprint_id": 2358, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": "SBK-THESIS.pdf", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "final", "relation": { "items": [ { "type": "http://eprints.org/relation/hasVolatileVersion", "uri": "/id/document/21050" }, { "type": "http://eprints.org/relation/haspreviewThumbnailVersion", "uri": "/id/document/21050" }, { "type": "http://eprints.org/relation/hasVersion", "uri": "/id/document/21050" } ] } }, { "id": "/id/document/21050", "doc_id": 21050, "rev_number": 2, "files": [ { "id": "/id/file/25828", "fileid": 25828, "datasetid": "document", "objectid": 21050, "filename": "preview.png", "mime_type": "image/png", "hash": "6b9e72e09b00a070523995fa00cdc255", "hash_type": "MD5", "filesize": 10087, "mtime": "2012-12-26 02:50:33", "url": "/2358/2/preview.png" } ], "eprint_id": 2358, "pos": 2, "placement": 2, "mime_type": "image/png", "format": "image/png", "language": "en", "security": "public", "license": "other", "main": "preview.png", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/4484" }, { "type": "http://eprints.org/relation/ispreviewThumbnailVersionOf", "uri": "/id/document/4484" }, { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/4484" } ] } }, { "id": "/id/document/122746", "doc_id": 122746, "rev_number": 1, "files": [ { "id": "/id/file/368144", "fileid": 368144, "datasetid": "document", "objectid": 122746, "filename": "indexcodes.txt", "mime_type": "text/plain", "hash": "f12f44690e344d9bfb3dfb2662ce75b7", "hash_type": "MD5", "filesize": 22639, "mtime": "2021-06-23 22:06:07", "url": "/2358/3/indexcodes.txt" } ], "eprint_id": 2358, "pos": 3, "placement": 3, "mime_type": "text/plain", "format": "other", "format_desc": "Generate index codes conversion from application/pdf to indexcodes", "language": "en", "security": "public", "license": "other", "main": "indexcodes.txt", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/4484" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/4484" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/4484" } ] } } ], "eprint_status": "archive", "userid": 2, "dir": "disk0/00/00/23/58", "datestamp": "2005-06-01", "lastmod": "2020-06-16 18:51:32", "status_changed": "2009-09-25 02:35:37", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Klamo-Sara-Bernadine", "name": { "family": "Klamo", "given": "Sara Bernadine" }, "show_email": "NO" } ] }, "title": "Direct Examination of Initiation and Propagation Kinetics of Zirconocene-Catalyzed Alkene Polymerization", "ispublished": "unpub", "full_text_status": "public", "keywords": "alkene polymerization; mechanism; metallocene", "abstract": "Zirconocene precatalysts with sterically bulky alkyl groups were designed in order to obtain models for the propagating species in zirconocene-catalyzed alkene polymerization. Alkyllithium reagents Li(CH2CEt3) and Li(CH2CMe2CH2Ph) were prepared and utilized in methyl alkylzirconocene synthesis. Dialkyl and methyl alkylzirconocenes of the form [(eta-5-C5H5) (eta-5-C5Me5)Zr(R)2], [(eta-5-C5H5)2Zr(R)(CH3)], and [(eta-5-C5H5)(eta-5-C5Me5)Zr(R)(CH3)] (where R = CH2CMe3, CH2SiMe3, CH2CEt3,CH2CMe2CH2Ph) were synthesized and fully characterized by NMR spectroscopy and in some cases X-ray diffraction. The molecular structures determined display the bent sandwich coordination mode common for zirconocenes. The observed structural parameters are slightly perturbed by the steric influence of the bulky alkyl group.
\r\n\r\nA direct examination of propagation kinetics for alkene polymerization using the zirconocenium initiator, [(eta-5-C5H5)(eta-5-C5Me5)Zr(CH2CMe3)]+[CH3B(C6F5)3]-, is reported. Propagation rate constants (kp) for the polymerization of propene and a series of 1-alkenes catalyzed by [(eta-5-C5H5)(eta-5-C5Me5)Zr(CH2CHR)nCH2CMe3)]+[CH3B(C6F5)3]- were measured by 1H NMR spectroscopy in toluene-d8 at low temperature. The kp obtained for propene and other alkenes decreases with increasing chain length and steric influence. The overall activation parameters for propagation determined from an Eyring analysis are (delta)H(activation) = 8.5(3) kcal/mol and (delta)S(activation) = -25(2) eu. The propagation rate was found to increase in the presence of [CH3B(C6F5)3]- counteranion and in a polar toluene-d8-chlorobenzene-d5 solvent system. The experimental results are most consistent with propagation mechanism that does not involve the formation of outer-sphere ions for alkene polymerization by this catalyst system.
\r\n\r\nPropene initiation kinetics have been examined for a series of alkylzirconocene initiators, [(eta-5-C5H5)(eta-5-C5Me5)Zr(R)]+[CH3B(C6F5)3]- (R = CH3 (5), CH2CMe3 (1), CH2SiMe3 (4)). Measurement of ki for the neopentyl initiator reveals that the rate of initiation is on the order of propagation for this catalyst. This initiator with a polymeryl like alkyl group serves as a model of the propagating species in propene polymerization. The catalyst initiation behavior has been investigated and the observed relative rates of propene initiation are not always predicted by ground-state (zirconium-carbon bond strength or extent of ion-pairing) considerations. The catalysts 4 and 5 are both poor initiators with ki << kp and show less than 50% initiation in the presence of excess propene at -60 C in toluene-d8.
", "date": "2005", "date_type": "degree", "id_number": "CaltechETD:etd-06012005-144620", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechETD:etd-06012005-144620", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "deposited_by": "Imported from ETD-db", "deposited_on": "2005-06-01", "doi": "10.7907/Z24R-FF38", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "rhg@its.caltech.edu", "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "role": "chair" }, { "email": "stoltz@caltech.edu", "id": "Stoltz-B-M", "name": { "family": "Stoltz", "given": "Brian M." }, "role": "member" }, { "email": "hgcm@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "member" }, { "email": "Bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_submitted_date": "2005-06-01", "thesis_defense_date": "2005-05-27", "thesis_approved_date": "2005-06-01", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive\nlicense to archive and make accessible, under the conditions specified below,\nmy thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "2005", "author_list": "Klamo, Sara Bernadine", "advisor_list": "Bercaw, John E.", "comittee_list": "Grubbs, Robert H.; Stoltz, Brian M.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/2387", "eprint_id": 2387, "rev_number": 10, "documents": [ { "id": "/id/document/4532", "doc_id": 4532, "rev_number": 3, "files": [ { "id": "/id/file/26122", "fileid": 26122, "datasetid": "document", "objectid": 4532, "filename": "JSOTHESISFINAL.pdf", "mime_type": "application/pdf", "filesize": 6850326, "mtime": "2012-12-26 02:50:50", "url": "/2387/1/JSOTHESISFINAL.pdf" } ], "eprint_id": 2387, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": "JSOTHESISFINAL.pdf", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "final", "relation": { "items": [ { "type": "http://eprints.org/relation/hasVolatileVersion", "uri": "/id/document/21095" }, { "type": "http://eprints.org/relation/haspreviewThumbnailVersion", "uri": "/id/document/21095" }, { "type": "http://eprints.org/relation/hasVersion", "uri": "/id/document/21095" } ] } }, { "id": "/id/document/21095", "doc_id": 21095, "rev_number": 2, "files": [ { "id": "/id/file/26120", "fileid": 26120, "datasetid": "document", "objectid": 21095, "filename": "preview.png", "mime_type": "image/png", "hash": "57da9081f35c090f2307c5794a6b8069", "hash_type": "MD5", "filesize": 11149, "mtime": "2012-12-26 02:50:49", "url": "/2387/2/preview.png" } ], "eprint_id": 2387, "pos": 2, "placement": 2, "mime_type": "image/png", "format": "image/png", "language": "en", "security": "public", "license": "other", "main": "preview.png", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/4532" }, { "type": "http://eprints.org/relation/ispreviewThumbnailVersionOf", "uri": "/id/document/4532" }, { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/4532" } ] } }, { "id": "/id/document/122794", "doc_id": 122794, "rev_number": 1, "files": [ { "id": "/id/file/368192", "fileid": 368192, "datasetid": "document", "objectid": 122794, "filename": "indexcodes.txt", "mime_type": "text/plain", "hash": "56292524f77f24a70e3d02d6a0ac05df", "hash_type": "MD5", "filesize": 24086, "mtime": "2021-06-23 22:07:58", "url": "/2387/3/indexcodes.txt" } ], "eprint_id": 2387, "pos": 3, "placement": 3, "mime_type": "text/plain", "format": "other", "format_desc": "Generate index codes conversion from application/pdf to indexcodes", "language": "en", "security": "public", "license": "other", "main": "indexcodes.txt", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/4532" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/4532" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/4532" } ] } } ], "eprint_status": "archive", "userid": 2, "dir": "disk0/00/00/23/87", "datestamp": "2005-06-03", "lastmod": "2020-06-16 19:30:29", "status_changed": "2009-09-25 02:36:15", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "jso2115@columbia.edu", "id": "Owen-Jonathan-Scharle", "name": { "family": "Owen", "given": "Jonathan Scharle" }, "orcid": "0000-0001-5502-3267", "show_email": "NO" } ] }, "title": "A Study of Ligand Substitution and its Importance in the C-H Activation of Methane and Methanol", "ispublished": "unpub", "full_text_status": "public", "keywords": "Alkane Activation; Aminocarbene; Carbene; Ligand Substitution; Methane; Platinum", "abstract": "Pyridinium and indolium-derived aminocarbene complexes of platinum and palladium were prepared by oxidative addition of pyridinium and 2-chloro-indolium carbene precursors. These complexes were synthesized in order to study the degree to which aminocarbene ligands pi-bond with the transition-metals to which they are bound. X-Ray crystal structures show minimal multiple bonding in the indole examples and a measurable shortening of the pyridine-2-ylidene Pt\u2013C distance (1.959(3) A) compared with typical Pt\u2013C bonds (2.01(1) A). The kinetics of associative DMSO substitution trans to the pyridine-2-ylidene ligand indicate a stabilization of the trigonal bipyramidal transition structure that is due to pi-acidity of the carbene carbon. This pi-acidity is responsible for 4-orders of magnitude acceleration in the associative substitution rate compared with a structurally similar phenyl donor.
\r\n\r\nThe relative rates of methane, methanol and dimethylether C\u2013H activation by [(N-N)PtMe(TFE-d3)]+ ((N-N) = ArN=C(Me)-C(Me)=NAr Ar = 3,5-di-tert-butylphenyl, TFE-d3 = CF3CD2OD) were studied by 1H and 13C NMR spectroscopy. Methane activation kinetics were conducted at 300-1000 psi of methane pressure in single crystal sapphire NMR tubes (k = 1.6 \u00b1 0.4 x 10-3 M-1s-1, 330 K; k = 2.7 \u00b1 0.2 x 10-4 M-1s-1, 313 K). Deuterium scrambling studies indicate that displacement of TFE-d3 from the platinum center by methane's C\u2013H bond is slower than the subsequent C\u2013H oxidative cleavage and hence the rate-determining step in methane C\u2013H activation. The kinetics of methanol and dimethylether C\u2013H activation were studied with 1H NMR spectroscopy and shown to be inhibited by a preequilibrium binding of the substrates oxygen lone-pair to the metal center. A small kinetic isotope effect (kH/kD = 1.4 \u00b1 0.1) and the observed concentration dependence suggest that the reaction proceeds by rate determining displacement of the coordinated trifluoroethanol by the C-H bonds of methanol (k = 2.0 \u00b1 0.2 x 10-3 M-1s-1, Keq = 0.0042 \u00b1 0.0006, 330 K). A similar concentration dependence is observed in the activation of dimethylether (k = 5.5 \u00b1 0.5 x 10-4 M-1s-1, Keq = 0.020 \u00b1 0.002, 313 K). Comparison of these second order rate constants (k(Methane)/k(Methanol) = 1/1.3, 330 K; k(Methane)/k(Dimethylether) = 1/2, 313 K) shows that the selectivity of this ligand substitution step matches the selectivity previously reported by our group for oxidizing methyl and hydroxymethyl groups with aqueous tetrachloroplatinate (1/1.5). These data strongly suggest a similar rate-determining step under the Shilov conditions.
", "date": "2005", "date_type": "degree", "id_number": "CaltechETD:etd-06022005-124848", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechETD:etd-06022005-124848", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "deposited_by": "Imported from ETD-db", "deposited_on": "2005-06-03", "doi": "10.7907/1SHC-4G39", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" }, { "id": "Labinger-J-A", "name": { "family": "Labinger", "given": "Jay A." }, "role": "co-advisor" } ] }, "thesis_committee": { "items": [ { "email": "stoltz@caltech.edu", "id": "Stoltz-B-M", "name": { "family": "Stoltz", "given": "Brian M." }, "role": "chair" }, { "email": "jal@caltech.edu", "id": "Labinger-J-A", "name": { "family": "Labinger", "given": "Jay A." }, "role": "member" }, { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" }, { "email": "rhg@caltech.edu", "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_submitted_date": "2005-06-02", "thesis_defense_date": "2005-05-27", "thesis_approved_date": "2005-06-03", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive\nlicense to archive and make accessible, under the conditions specified below,\nmy thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "2005", "author_list": "Owen, Jonathan Scharle", "advisor_list": "Bercaw, John E. and Labinger, Jay A.", "comittee_list": "Stoltz, Brian M.; Labinger, Jay A.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/2444", "eprint_id": 2444, "rev_number": 24, "documents": [ { "id": "/id/document/4645", "doc_id": 4645, "rev_number": 3, "files": [ { "id": "/id/file/26786", "fileid": 26786, "datasetid": "document", "objectid": 4645, "filename": "Ch1.pdf", "mime_type": "application/pdf", "filesize": 2171749, "mtime": "2012-12-26 02:51:29", "url": "/2444/1/Ch1.pdf" } ], "eprint_id": 2444, "pos": 1, "placement": 2, "mime_type": "application/pdf", "format": "application/pdf", "format_desc": "Ch1.pdf", "language": "en", "security": "public", "license": "other", "main": "Ch1.pdf", "media_duration": "0", 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"media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/4648" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/4648" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/4648" } ] } } ], "eprint_status": "archive", "userid": 2, "dir": "disk0/00/00/24/44", "datestamp": "2004-06-07", "lastmod": "2021-02-03 00:04:18", "status_changed": "2009-09-25 02:37:38", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Schofer-Susan-Jessica", "name": { "family": "Schofer", "given": "Susan Jessica" }, "show_email": "NO" } ] }, "title": "The Effect of Ligand Array on Stereocontrol and Molecular Weight in Metallocene-Catalyzed \u03b1-Olefin Polymerization and (PNP)CrPh\u2083 Complexes as Well-Defined Ethylene Trimerization Catalysts", "ispublished": "unpub", "full_text_status": "public", "keywords": "chromium catalyst; ethylene trimerization; scandocene; stereocontrol in metallocene-catalyzed olefin poly; tetramethylaluminate; zirconocene", "abstract": "A series of neutral and cationic group 4 and neutral group 3 model complexes of the Me\u2082Si(\u03b7\u2075-C\u2085H\u2084)(\u03b7\u2075-3-(CMe\u2083)-C\u2085H\u2083)(tBuSp) ligand have been prepared: tBuSpZrCl\u2082(1), tBuSpZr(CH\u2082SiMe\u2083)\u2082 (8), tBuSpZrMe\u2082 (9), [tBuSpZrH\u2082]\u2082 (10), tBuSpZrMeCl (11), tBuSpZrMe(CH\u2082CMe\u2083) (12), tBuSpZrMe(CH\u2082SiMe\u2083) (13), tBuSpScCl(THF) (14), tBuSpScCH(SiMe\u2083)\u2082 (17), [tBuSpScH] (18), and tBuSpTiCl\u2082 (19). The kinetically preferred isomers of 12 and 13 have been identified, and in both cases the syn isomer is preferred. We have obtained solid state structures of [tBuSpZrH\u2082]\u2082 (10), tBuSpZrMeCl (11), tBuSpZrMe(CH\u2082CMe\u2083) (12), and tBuSpScCl(THF) (14). Complexes 12 and 13 isomerize to form predominantly the thermodynamically preferred anti isomers. The ratio of isomers observed for [tBuSpZrMe]\u207a[MeB(C\u2086F\u2085)\u2083]\u207b (21) and [tBuSpZrCH\u2082SiMe\u2083]\u207a[Me B(C\u2086F\u2085)\u2083]\u207b (22) suggests that the tBuSp ligand does not distinguish very well between different groups in the metallocene wedge ([delta]G = 0.27-0.89 kcal/mol). The tBu group is not an effective stereodirector in the ground state structures and the remarkable stereodirecting capability of this ligand in propylene polymerizations must be reconciled by its effect on transition state energies.
\r\n\r\nA series of scandocene tetramethylaluminate have been prepared, including Ind\u2082Sc(\u03bc-Me)\u2082AlMe\u2082 (1), Cp\u2082Sc(\u03bc-Me)\u2082AlMe\u2082 (2), Cp*CpSc(\u03bc-Me)\u2082AlMe\u2082 (3), and meso-DpSc(\u03bc-Me)\u2082AlMe\u2082 (4). These complexes display characteristic terminal and bridging methyl resonances in solution at room temperature, indicating static structures. Complexes 1-4 oligomerize 1-pentene to form a range of oligomers. The tetramethylaluminate complexes initiate oligomerization from a scandium-methyl species after dissociation of AlMe\u2083, and the primary mechanism of chain transfer is \u03b2-hydrogen elimination. Complexes 1-4 react with L donors (L = DMAP, THF, PMe\u2083) to form (RnCp)\u2082ScMe(L) compounds (5-9).
\r\n\r\nTo study the chromium-based ethylene trimerization catalyst involving the diphosphine ligand (o-MeO-C\u2086H\u2084)\u2082PN(Me)P(o-MeO-C\u2086H\u2084)\u2082 (PNPOMe (1)), we have synthesized (PNPOMe-d\u2081\u2082)CrPh\u2083 (11), (PNPSMe-d12)CrPh\u2083, (12), and (PNPOMe-d12)CrPh2Cl (14) containing deuterated PNP ligands. Activation of 11 by protonation with H\u207a(OEt\u2082)\u2082B[C\u2086H\u2083(CF\u2083)\u2082]\u2084- in the presence of ethylene provides an active trimerization catalyst that gives similar selectivity and activity to 1-hexene as the originally reported system and represents the first examples of an active, well-defined trimerization catalyst based on chromium. The trimerization of a 1:1 mixture of C\u2082H\u2084 and C\u2082D\u2084 gives only C\u2086D\u2081\u2082, C\u2086D\u2088H\u2084, C\u2086D\u2084H\u2088, and C\u2086H\u2081\u2082, the 1-hexene isotopomers without H/D scrambling, which is consistent with a trimerization mechanism involving metallacyclic intermediates.
", "date": "2004", "date_type": "degree", "id_number": "CaltechETD:etd-06042004-173118", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechETD:etd-06042004-173118", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "deposited_by": "Imported from ETD-db", "deposited_on": "2004-06-07", "doi": "10.7907/F04S-0S62", "alt_title": { "items": [ "The Effect of Ligand Array on Stereocontrol and Molecular Weight in Metallocene-Catalyzed alpha-Olefin Polymerization and (PNP)CrPh3 Complexes as Well-Defined Ethylene Trimerization Catalysts" ] }, "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "tirrell@caltech.edu", "id": "Tirrell-D-A", "name": { "family": "Tirrell", "given": "David A." }, "role": "chair" }, { "email": "Bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" }, { "email": "jpeters@caltech.edu", "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "role": "member" }, { "email": "rhg@its.caltech.edu", "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_submitted_date": "2004-06-04", "thesis_defense_date": "2004-05-28", "thesis_approved_date": "2004-06-07", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive\nlicense to archive and make accessible, under the conditions specified below,\nmy thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "2004", "author_list": "Schofer, Susan Jessica", "advisor_list": "Bercaw, John E.", "comittee_list": "Tirrell, David A.; Bercaw, John E.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/1906", "eprint_id": 1906, "rev_number": 23, "documents": [ { "id": "/id/document/3270", "doc_id": 3270, "rev_number": 4, "files": [ { "id": "/id/file/19498", "fileid": 19498, "datasetid": "document", "objectid": 3270, "filename": "Chapter1.pdf", "mime_type": "application/pdf", "filesize": 669047, "mtime": "2012-12-26 02:44:00", "url": "/1906/1/Chapter1.pdf" } ], "eprint_id": 1906, "pos": 1, "placement": 3, "mime_type": "application/pdf", "format": "application/pdf", "format_desc": "Chapter1.pdf", "language": "en", "security": "public", "license": "other", "main": "Chapter1.pdf", "media_duration": "0", 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"media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/3272" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/3272" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/3272" } ] } }, { "id": "/id/document/121570", "doc_id": 121570, "rev_number": 1, "files": [ { "id": "/id/file/366962", "fileid": 366962, "datasetid": "document", "objectid": 121570, "filename": "indexcodes.txt", "mime_type": "text/plain", "hash": "23ee2c4c0bf776cf183813bc01f8bd9d", "hash_type": "MD5", "filesize": 21552, "mtime": "2021-06-23 21:30:00", "url": "/1906/18/indexcodes.txt" } ], "eprint_id": 1906, "pos": 18, "placement": 18, "mime_type": "text/plain", "format": "other", "format_desc": "Generate index codes conversion from application/pdf to indexcodes", "language": "en", "security": "public", "license": "other", "main": "indexcodes.txt", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/63587" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/63587" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/63587" } ] } } ], "eprint_status": "archive", "userid": 2, "dir": "disk0/00/00/19/06", "datestamp": "2003-05-22", "lastmod": "2021-02-12 23:50:41", "status_changed": "2009-09-25 02:19:32", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "ljacker@yahoo.com", "id": "Ackerman-Lily-Joy", "name": { "family": "Ackerman", "given": "Lily Joy" }, "show_email": "NO" } ] }, "title": "Ancillary Ligand Effects in Niobocene Olefin Hydride Complexes and Hydrocarbon Oxidation by Palladium(II) Complexes", "ispublished": "unpub", "full_text_status": "public", "keywords": "hydrocarbon oxidation; niobium; olefin insertion; palladium", "abstract": "To examine the effects of cyclopentadienyl and olefin substitution on preferred stereochemistry, the preparation of a series of singly bridged ansa-niobocene olefin hydride complexes is described. These complexes serve as stable transition state analogues for the much more kinetically labile group 4 metallocenium cationic intermediates in metallocene-catalyzed olefin polymerization. Characterization of the thermodynamically preferred isomers of niobocene olefin hydride complexes reveals that placement of a single alkyl substituent on the cyclopentadienyl ligand array may have a moderate effect on the stereochemistry of olefin coordination.
\r\n\r\nUsing dynamic NMR methods the rates of hydrogen exchange following intramolecular ethylene insertion into the metal-hydride bond have been measured for singly and doubly bridged group 5 ansa-metallocene complexes. The singly bridged ansa-niobocenes exchange up to 3 orders of magnitude faster than unbridged complexes. However, the doubly bridged ansa-tantalocene complex exchanges at a rate comparable to that previously reported for the unlinked and much slower than a singly bridged complex. These \"ansa-effects\" were investigated by DFT calculations on model complexes. The computed exchange pathway showed the presence of an agostic ethyl intermediate. The calculated barriers for hydrogen exchange of model unbridged, singly bridged, and doubly bridged niobocenes correlate with the experimental results.
\r\n\r\nN,N'-Diaryl-diimine-ligated Pd(II) dimethyl complexes undergo protonolysis with tetrafluoroboric acid (aq) in trifluoroethanol (TFE) to form cationic monomethyl complexes and methane. The cations activate benzene C-H bonds at room temperature. Kinetic analyses reveal trends similar to those observed for the analogous Pt complexes: the C-H activation step is rate determining and is inhibited by water, which is consistent with a mechanism in which benzene substitution proceeds by a solvent- (TFE-) assisted associative pathway. After benzene C-H activation under 1 atm dioxygen, the products of the reaction are biphenyl and a dimeric hydroxide complex. The Pd(0) formed in the reaction is reoxidized by dioxygen after the oxidative C-C bond formation. Toluene and trifluorotoluene were investigated as substrates to examine the regioselectivity of arene coupling.
\r\n", "date": "2003", "date_type": "degree", "id_number": "CaltechETD:etd-05212003-130334", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechETD:etd-05212003-130334", "related_url": { "items": [ { "description": "Article adapted for ch. 1", "type": "doi", "url": "http://dx.doi.org/10.1021/om020628d" }, { "description": "Article adapted for ch. 2", "type": "doi", "url": "http://dx.doi.org/10.1021/om0206296" }, { "description": "Article adapted for ch. 3", "type": "doi", "url": "http://dx.doi.org/10.1021/om0303294" } ] }, "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "deposited_by": "Imported from ETD-db", "deposited_on": "2003-05-22", "doi": "10.7907/FZMS-V955", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "rhg@caltech.edu", "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "role": "chair" }, { "email": "stoltz@caltech.edu", "id": "Stoltz-B-M", "name": { "family": "Stoltz", "given": "Brian M." }, "role": "member" }, { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "member" }, { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_submitted_date": "2003-05-21", "thesis_defense_date": "2003-05-14", "thesis_approved_date": "2003-05-22", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive\nlicense to archive and make accessible, under the conditions specified below,\nmy thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "2003", "author_list": "Ackerman, Lily Joy", "advisor_list": "Bercaw, John E.", "comittee_list": "Grubbs, Robert H.; Stoltz, Brian M.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/6900", "eprint_id": 6900, "rev_number": 22, "documents": [ { "id": "/id/document/14517", "doc_id": 14517, "rev_number": 5, "files": [ { "id": "/id/file/93287", "fileid": 93287, "datasetid": "document", "objectid": 14517, "filename": "Wong-Foy_ag_2002.pdf", "mime_type": "application/pdf", "filesize": 5217076, "mtime": "2012-12-26 04:41:26", "url": "/6900/1/Wong-Foy_ag_2002.pdf" } ], "eprint_id": 6900, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": "Wong-Foy_ag_2002.pdf", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "final", "relation": { "items": [ { "type": "http://eprints.org/relation/hasVolatileVersion", "uri": "/id/document/27897" }, { "type": "http://eprints.org/relation/haspreviewThumbnailVersion", "uri": "/id/document/27897" }, { "type": "http://eprints.org/relation/hasVersion", "uri": "/id/document/27897" } ] } }, { "id": "/id/document/14518", "doc_id": 14518, "rev_number": 4, "files": [ { "id": "/id/file/207817", "fileid": 207817, "datasetid": "document", "objectid": 14518, "filename": "Wong-Foy_ag_2002.zip", "mime_type": "application/zip", "filesize": 4903283, "mtime": "2016-08-22 21:23:45", "url": "/6900/2/Wong-Foy_ag_2002.zip" } ], "eprint_id": 6900, "pos": 2, "format": "application/zip", "format_desc": "TIFF", "language": "en", "security": "internal", "license": "other", "main": "Wong-Foy_ag_2002.zip", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "archival" }, { "id": "/id/document/27897", "doc_id": 27897, "rev_number": 3, "files": [ { "id": "/id/file/93285", "fileid": 93285, "datasetid": "document", "objectid": 27897, "filename": "preview.png", "mime_type": "image/png", "hash": "1e8bd783cbabdad31dec8f9567bce470", "hash_type": "MD5", "filesize": 19307, "mtime": "2012-12-26 04:41:26", "url": "/6900/3/preview.png" } ], "eprint_id": 6900, "pos": 3, "placement": 3, "mime_type": "image/png", "format": "image/png", "language": "en", "security": "public", "license": "other", "main": "preview.png", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/14517" }, { "type": "http://eprints.org/relation/ispreviewThumbnailVersionOf", "uri": "/id/document/14517" }, { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/14517" } ] } } ], "eprint_status": "archive", "userid": 51, "dir": "disk0/00/00/69/00", "datestamp": "2012-04-11 18:22:08", "lastmod": "2022-11-07 23:44:27", "status_changed": "2022-11-07 23:44:27", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Wong-Foy-Antek-Golangco", "name": { "family": "Wong-Foy", "given": "Antek Golangco" }, "show_email": "NO" } ] }, "title": "Ancillary Ligand Effects in Zirconium(IV) Aminoborollide and Nitrogen Chelated Pt(II) Complexes", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "The preparation of new chloro derivatives of pentamethylcyclopentadienyl aminoborollide complexes of Zr are described. Treatment of the dianions 1.9-1.12 with Cp*ZrCl_3 yields Cp*{\u03b7^5-C_4H_4BN(Si(CH_3)_3)_2}ZrCl\u2022LiCl (1.13), Cp*{\u03b7^5-C_4H_4BNC(CH_3)_3Si(CH_3)_3}ZrCl\u2022Li\u2022CI (1.14). |Cp*{\u03b7^5-C_4H_4BN(Et)CH_2CH_2Net_2}ZrCl_2Li]_2 (1.15), and Cp*{\u03b7^5-2,5-Ph_2C_4H_2BNMe_2}ZrCl\u2022LiCl (1.16). The electronic spectra of these complexes were measured and compared to the parent complex Cp*{\u03b7^5-C_4H_4BN(CHMe_2)_2}ZrCl\u2022LiCl (1.17a) in THF solvent. In general, as the substituents directly bonded to nitrogen increase in size, a blue shift of the low energy, aminoborollide to zirconium charge transfer band (LMCT), occurs. \u03bb_(max) decreases in the order 1.16 > 1.17a > 1.14 > 1.15 ~ 1.13. The anionic portions of complexes 1.13-1.16 have also been structurally characterized by x-ray crystallography. Although the changes are very small, in general a lengthened B-N bond correlates linearly with the observed blue shift of the LMCT band.
\r\n\r\nStudies directed towards the development of a Pt(II)-catalyzcd oxidation of ethylene to ethylene\r\nglycol based on the Shilov system for alkane functionalization is described. The first step is the activation of ethylene towards nucleophilic attack by water to generate a Pt(II) \u03b2-hydroxyalkyl intermediate that is oxidized in a second step to the Pt(IV) \u03b2-hydroxyalkyl. Reductive elimination via an S_N2-type mechanism at the \u03b1-C of the Pt(IV) \u03b2-hydroxyalkyl liberates the oxidized product leaving the reduced Pt(II) center to bind another equivalent of olefin. The first system examined was the methyl ethylene complex [(tmeda)PtMe(\u03b7^2-C_2H_4)][SbF_6,], 2.2. Nucleophilic attack at the bound ethylene was not observed: instead displacement of ethylene occurred. The bound ethylene in the neutral complexes cis-Cl_2PtL(\u03b7^2-C_2H_4), (L =PPh_3 (2.23), AsPh_3 (2.24), Me_2SO (2.25)) and trans-Cl_2Pt(\u03b7^2-C_2CH_4)(C_5H_5N). 2.26 arc susceptible towards attack by OH-. Under catalytic conditions (excess ethylene and H_2O_2) decomposition of 2.23, 2.24, and 2.25 was observed. In 2.26, 1 turnover was observed before decomposition occurred. The hound ethylene in the complex [(tmeda)PtCl(\u03b7^2-C_2H_4)][ClO_4] is activated towards nucleophilic attack by water and OH-, allowing the isolation of the Pt(II) \u03b2-hydroxyalkyl. This is rapidly oxidized to the Pt(IV) \u03b2-hydroxyalkyl by hydrogen peroxide. In the presence of HCl, it undergoes reductive elimination to yield 2-chlorocthanol\r\nand (tmeda)PtCl_2. Unfortunately, this system also showed no catalytic activity.
\r\n\r\nThe dicationic complexes (|(ArN=C(Me)-C(Me)=NAr)Pt(solv)_2 |X_2. (\u039br = 2.6-(CH_3)_2C_6,H_3: 3.5a:\r\nsolv = CH_3CN, X = CF_3SO_3-, BF_4-, SbF_6-; 3.5b: solv = (CH_3)_2CO, X = BF_4-, SbF_6-,) and 3.6\r\n[(CyN=C(H)-C(H)=NCy)Pt(CH_3CN)_2]X_2, (Cy = C_6H_(11) , X= OTf, BF_4-, Pf_6-, SbF_6-) were synthesized from the corresponding Pt dichlorides with 2 equiv. of AgX. The reaction of 3.5a with 1-phenylpyrazole, 2-phenylpyridine, 2-vinylpyridine, and 2-(2-thienyl)pyridine in acetone affords the cyclometalation products 3.11-3.14 via intramolecular C-H activation of an sp^2 C-H bond of the unsaturated sidegroup. Pyridines with saturated groups at the 2-position do not undergo a similar cyclomctalation reaction. 3.6 undergoes cyclometalation of one of the cyclohexyl groups, an example of sp^3 C-H bond activation. The later reaction proceeds only partway to completion, implying that an equilibrium has been reached: in the case where X = OTf, the equilibrium favors the starting dication. Furthermore, the intramolecular C-H activation occurs in trifluoroethanol but not in acetone under comparable conditions in contrast to the reactions of 3.5a with\r\nthe substituted pyridines.
\r\n\r\nThe diaqua complexe [(ArN=C(Me)-C(Me)=NAr)Pt(H_2O)_2]X_2, 4.3. (\u039br = 2.6-(CH_3)_2C_6H_3; X = OTf^-, BF_4^-) decompose in aqueous solution to yield a red-orange precipitate. Spectroscopic characterization of the precipitate by ^1H, IR, and conductivity measurements is consistent with C_(2v), symmetric structure containing hydroxo groups. Confirmation of the dicationic, dinuclear Pt(II) complex, 4.4, where the two Pt centers are bridged by two OH groups was revealed by x-ray crystallography.
", "date": "2002", "date_type": "degree", "id_number": "CaltechTHESIS:04102012-133622013", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:04102012-133622013", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Ben Perez", "deposited_by": "Tony Diaz", "deposited_on": "2012-04-11 18:22:08", "doi": "10.7907/6xyc-e660", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "orcid": "0000-0002-0057-7817", "role": "chair" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876", "role": "member" }, { "id": "Rees-D-C", "name": { "family": "Rees", "given": "Douglas C." }, "orcid": "0000-0003-4073-1185", "role": "member" }, { "id": "Labinger-J-A", "name": { "family": "Labinger", "given": "Jay A." }, "role": "member" }, { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "2001-10-01", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "2002", "author_list": "Wong-Foy, Antek Golangco", "advisor_list": "Bercaw, John E.", "comittee_list": "Grubbs, Robert H.; Gray, Harry B.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/8167", "eprint_id": 8167, "rev_number": 22, "documents": [ { "id": "/id/document/46899", "doc_id": 46899, "rev_number": 3, "files": [ { "id": "/id/file/137486", "fileid": 137486, "datasetid": "document", "objectid": 46899, "filename": "ZHONG 2001.pdf", "mime_type": "application/pdf", "hash": "d255bc6211338fee9221755b8b72a35f", "hash_type": "MD5", "filesize": 53986796, "mtime": "2014-03-25 21:05:17", "url": "/8167/1/ZHONG 2001.pdf" } ], "eprint_id": 8167, "pos": 1, "placement": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": 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"content": "final" }, { "id": "/id/document/128876", "doc_id": 128876, "rev_number": 1, "files": [ { "id": "/id/file/374312", "fileid": 374312, "datasetid": "document", "objectid": 128876, "filename": "indexcodes.txt", "mime_type": "text/plain", "hash": "8918e903f377db6d83eeb45d724a08e4", "hash_type": "MD5", "filesize": 44972, "mtime": "2021-06-24 03:18:15", "url": "/8167/8/indexcodes.txt" } ], "eprint_id": 8167, "pos": 8, "placement": 8, "mime_type": "text/plain", "format": "other", "format_desc": "Generate index codes conversion from application/pdf to indexcodes", "language": "en", "security": "public", "license": "other", "main": "indexcodes.txt", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/46899" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/46899" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/46899" } ] } } ], "eprint_status": "archive", "userid": 50, "dir": "disk0/00/00/81/67", "datestamp": "2014-03-26 16:56:05", "lastmod": "2022-11-30 00:18:26", "status_changed": "2014-03-26 16:56:05", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Zhong-Hong-A", "name": { "family": "Zhong", "given": "Hong A." }, "show_email": "NO" } ] }, "title": "Ancillary Ligand Effects: From Zirconium(IV)-Catalyzed Homogeneous Propylene Polymerization to Platinum(II)-Mediated C-H Bond Activation", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "A series of Cs- and C1-symmetric doubly-linked ansa-metallocenes of the general formula {1,1'-SiMe2-2,2'-E-('\u019e5-C5H2-4-R1)-(\u019e5-C5H-3',5'-(CHMe2)2)}ZrC2 (E = SiMe2 (1), SiPh2 (2), SiMe2 -SiMe2 (3); R1 = H, CHMe2, C5H9, C6H11, C6H5) has been prepared. When activated by methylaluminoxane, these are active propylene polymerization catalysts. 1 and 2 produce syndiotactic polypropylenes, and 3 produces isotactic polypropylenes. Site epimerization is the major pathway for stereoerror formation for 1 and 2. In addition, the polymer chain has slightly stronger steric interaction with the diphenylsilylene linker than with the dimethylsilylene linker. This results in more frequent site epimerization and reduced\r\nsyndiospecificity for 2 compared to 1.
\r\n\r\nC1-Symmetric ansa-zirconocenes [1,1 '-SiMe2-(C5H4)-(3-R-C5H3)]ZrCl2 (4), [1,1 '-SiMe2-(C5H4)-(2,4-R2-C5H2)]ZrCl2 (5) and [1,1 '-SiMe2-2,2 '-(SiMe2-SiMe2)-(C5H3)-( 4-R-C5H2)]ZrCl2 (6) have been prepared to probe the origin of isospecificity in 3. While 4 and 3 produce polymers with similar isospecificity, 5 and 6 give mostly hemi-isotactic-like polymers. It is proposed that the facile site epimerization via an associative pathway allows rapid equilibration of the polymer chain between the isospecific and aspecific insertion sites. This results in more frequent insertion from the isospecific site, which has a lower kinetic barrier for chain propagation. On the other hand, site epimerization for 5 and 6 is slow. This leads to mostly alternating insertion from the isospecific and aspecific sites, and consequently, a hemi-isotactic-like polymers. In comparison, site epimerization is even slower for 3, but enchainment from the aspecific site has an extremely high kinetic barrier for monomer coordination. Therefore, enchainment occurs preferentially from the isospecific site to produce isotactic polymers.
\r\n\r\nA series of cationic complexes [(ArN=CR-CR=NAr)PtMe(L)]+[BF4]+ (Ar = aryl; R = H, CH3; L = water, trifluoroethanol) has been prepared. They react smoothly with benzene at approximately room temperature in trifluoroethanol solvent to yield methane and the corresponding phenyl Pt(II) cations, via Pt(IV)-methyl-phenyl-hydride intermediates. The reaction products of methyl-substituted benzenes suggest an inherent reactivity preference for aromatic over benzylic C-H bond activation, which can however be overridden by steric effects. For the reaction of benzene with cationic Pt(II) complexes, in which the diimine ligands bear 3,5-disubstituted aryl groups at the nitrogen atoms, the rate-determining step is C-H bond activation. For the more sterically crowded analogs with 2,6-dimethyl-substituted aryl groups, benzene coordination becomes rate-determining. The more electron-rich the ligand, as reflected by the CO stretching frequency in the IR spectrum of the corresponding cationic carbonyl complex, the faster the rate of C-H bond activation. This finding, however, does not reflect the actual C-H bond activation process, but rather reflects only the relative ease of solvent molecules displacing water molecules to initiate the reaction. That is, the change in rates is mostly due to a ground state effect. Several lines of evidence suggest that associative substitution pathways operate to get the hydrocarbon substrate into, and out of, the coordination sphere; i.e., that benzene substitution proceeds by a solvent- (TFE-) assisted associative pathway.
\r\n", "date": "2001", "date_type": "degree", "id_number": "CaltechTHESIS:03252014-134849293", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:03252014-134849293", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "deposited_on": "2014-03-26 16:56:05", "doi": "10.7907/km2k-bb61", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." }, "role": "chair" }, { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" }, { "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "orcid": "0000-0002-0057-7817", "role": "member" }, { "id": "MacMillan-D-W-C", "name": { "family": "MacMillan", "given": "David W. C." }, "orcid": "0000-0003-3352-4532", "role": "member" }, { "id": "Labinger-J-A", "name": { "family": "Labinger", "given": "Jay A." }, "orcid": "0000-0002-1942-9232", "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "2001-05-24", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "2001", "author_list": "Zhong, Hong A.", "advisor_list": "Bercaw, John E.", "comittee_list": "Anson, Fred C.; Bercaw, John E.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/8177", "eprint_id": 8177, "rev_number": 27, "documents": [ { "id": "/id/document/47144", "doc_id": 47144, "rev_number": 3, "files": [ { "id": "/id/file/137947", "fileid": 137947, "datasetid": "document", "objectid": 47144, "filename": "Wong 2001.pdf", "mime_type": "application/pdf", "hash": "f3fe3bd8cf4ddf1091692fa37d14387f", "hash_type": "MD5", "filesize": 15909227, "mtime": "2014-04-01 23:18:21", "url": "/8177/1/Wong 2001.pdf" } ], "eprint_id": 8177, "pos": 1, "placement": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": "Wong 2001.pdf", 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"/id/document/128906", "doc_id": 128906, "rev_number": 1, "files": [ { "id": "/id/file/374342", "fileid": 374342, "datasetid": "document", "objectid": 128906, "filename": "indexcodes.txt", "mime_type": "text/plain", "hash": "9f4eb6d69fe5c578a89b3ac61557e3d5", "hash_type": "MD5", "filesize": 28693, "mtime": "2021-06-24 03:19:18", "url": "/8177/7/indexcodes.txt" } ], "eprint_id": 8177, "pos": 7, "placement": 7, "mime_type": "text/plain", "format": "other", "format_desc": "Generate index codes conversion from application/pdf to indexcodes", "language": "en", "security": "public", "license": "other", "main": "indexcodes.txt", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/47144" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/47144" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/47144" } ] } } ], "eprint_status": "archive", "userid": 50, "dir": "disk0/00/00/81/77", "datestamp": "2014-04-02 16:15:19", "lastmod": "2022-11-30 00:10:46", "status_changed": "2014-04-02 16:15:19", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Wong-Chi-Kin", "name": { "family": "Wong", "given": "Chi-Kin" }, "show_email": "NO" } ] }, "title": "Spectroscopic Studies of Gas-Phase Molecular Clusters", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry\r\n\r\n", "abstract": "Spectroscopic investigations of hydrogen-bonding and van der Waals' interactions\r\nm molecular clusters were studied by the techniques of infrared predissociation and\r\nresonance-enhanced multiphoton ionization spectroscopies (REMPI). Ab initio\r\ncalculations were applied in conjunction for data interpretation.
\r\n\r\nThe infrared predissociation spectroscopy of CN^-\u2022(H_2O)_n (n = 2 - 6) clusters was\r\nreported in the region of 2950 - 3850 cm^(-1).\r\nThe hydrogen bondings for the C-site and N-site\r\nbinding, and among the water molecules were identified for n = 2 to 4. A spectral\r\ntransition was observed for n = 5 and 6, implying that the anion was surface-bound onto\r\nthe water aggregates in larger clusters.
\r\n\r\nThe infrared predissociation spectroscopy of Br^-\u2022(NH_3) and I^-\u2022(NH_3)_n (n =1-3)\r\nclusters was reported in the region of 3050-3450 cm^(-1).\r\nFor the Br^-\u2022(NH_3) complex, a\r\ndominating ionic NH stretch appeared at 3175 cm^(-1), and the weaker free NH stretch\r\nappeared at 3348 cm^(-1). The observed spectrum was consistent to the structure in which\r\nthere was one nearly linear hydrogen bond between Br^- and the NH_3 moiety. For the I^-\r\n\u2022(NH_3) complex, five distinct IR absorption bands were observed in the spectrum. The\r\nspectrum was not consistent with basic frequency patterns of three geometries considered\r\nin the ab initio calculations - complex with one, two and three hydrogen bondings\r\nbetween I^- and the NH_3 moiety. Substantial inhomogenous broadening were displayed in\r\nthe spectra for I^-\u2022(NH_3)_n (n =2-3), suggesting the presence of multiple isomers.
\r\n\r\nThe REMPI spectroscopy of the bound 4p ^2\u041f 1/2 and ^2\u041f 3/2 states, and the\r\ndissociative 3d ^2\u03a3^+ 1/2 state in the Al\u2022Ar complex was reported. The dissociative spectrum\r\nat Al^+ channel suggested the coupling of the 4p ^2\u041f 1/2,3/2 states to the repulsive 3d ^2\u03a3^+ 1/2\r\nstate. The spin-electronic coupling was further manifested in the dissociative Al^+\r\nspectrum of the 3d ^2\u03a3^+ 1/2 state. Using the potential energy curves obtained from ab initio\r\ncalculations, a bound \u2192 continuum Franck-Condon-intensity simulation was performed\r\nand compared with the one-photon 3d ^2\u03a3^+ 1/2 profile. The agreement provided evidence\r\nfor the petturbation above the Al(3d)Ar dissociation limit, and the repulsive character of\r\nthe 3d ^2\u03a3^+ 1/2 state.
\r\n", "date": "2001", "date_type": "degree", "id_number": "CaltechTHESIS:04012014-155631770", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:04012014-155631770", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Tony Diaz", "deposited_on": "2014-04-02 16:15:19", "doi": "10.7907/y9tk-8g51", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Okumura-M", "name": { "family": "Okumura", "given": "Mitchio" }, "orcid": "0000-0001-6874-1137", "role": "advisor" }, { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "co-advisor" } ] }, "thesis_committee": { "items": [ { "id": "Chan-S-I", "name": { "family": "Chan", "given": "Sunney I." }, "orcid": "0000-0002-5348-2723", "role": "chair" }, { "id": "Beauchamp-J-L", "name": { "family": "Beauchamp", "given": "Jesse L." }, "orcid": "0000-0001-8839-4822", "role": "member" }, { "id": "McKoy-B-V", "name": { "family": "McKoy", "given": "Basil Vincent" }, "role": "member" }, { "id": "Okumura-M", "name": { "family": "Okumura", "given": "Mitchio" }, "orcid": "0000-0001-6874-1137", "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "2000-06-26", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "2001", "author_list": "Wong, Chi-Kin", "advisor_list": "Okumura, Mitchio and Bercaw, John E.", "comittee_list": "Chan, Sunney I.; Beauchamp, Jesse L.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/1296", "eprint_id": 1296, "rev_number": 13, "documents": [ { "id": "/id/document/1963", "doc_id": 1963, "rev_number": 4, "files": [ { "id": "/id/file/12290", "fileid": 12290, "datasetid": "document", "objectid": 1963, "filename": "Chong_sh_2001.pdf", "mime_type": "application/pdf", "filesize": 4476745, "mtime": "2012-12-26 02:36:57", "url": "/1296/1/Chong_sh_2001.pdf" } ], "eprint_id": 1296, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": "Chong_sh_2001.pdf", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "final", "relation": { "items": [ { "type": "http://eprints.org/relation/hasVolatileVersion", "uri": "/id/document/18733" }, { "type": "http://eprints.org/relation/haspreviewThumbnailVersion", "uri": "/id/document/18733" }, { "type": "http://eprints.org/relation/hasVersion", "uri": "/id/document/18733" } ] } }, { "id": "/id/document/18733", "doc_id": 18733, "rev_number": 3, "files": [ { "id": "/id/file/12288", "fileid": 12288, "datasetid": "document", "objectid": 18733, "filename": "preview.png", "mime_type": "image/png", "hash": "15a2b67b209bc94ecedbe61c33f5438c", "hash_type": "MD5", "filesize": 13772, "mtime": "2012-12-26 02:36:57", "url": "/1296/2/preview.png" } ], "eprint_id": 1296, "pos": 2, "placement": 2, "mime_type": "image/png", "format": "image/png", "language": "en", "security": "public", "license": "other", "main": "preview.png", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/1963" }, { "type": "http://eprints.org/relation/ispreviewThumbnailVersionOf", "uri": "/id/document/1963" }, { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/1963" } ] } } ], "eprint_status": "archive", "userid": 2, "dir": "disk0/00/00/12/96", "datestamp": "2008-04-08", "lastmod": "2022-09-13 20:53:51", "status_changed": "2009-09-25 02:00:35", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Chong-Sing-Hwa", "name": { "family": "Chong", "given": "Sing Hwa" }, "show_email": "NO" } ] }, "title": "Ultrafast Dynamics of Barrier Crossing: Step-Wise Solvation Effect on Isomerization of Trans-Stilbene in Alkane Clusters", "ispublished": "unpub", "full_text_status": "public", "keywords": "(Chemistry)", "abstract": "The ultrafast spectroscopic study of molecular clusters in supersonic beams can provide valuable information on the structure, energetics and dynamics of molecular aggregates in gas phase and in solution. This information will shed light on important issues such as how molecules interact, how energy flows in solvated systems, and how chemical reactions progress.
\r\n\r\nAlthough microscopic friction and solvation in barrier crossing reactions is of fundamental importance in molecular dynamics, their roles are not well understood. This is mainly due to the fact that few comprehensive investigations of this subject have been performed. In this thesis, the detail studies of a prototypical barrier crossing reaction\u2014the photoisomerization of jet-cooled trans-stilbene\u2014in size-selected n-alkane clusters, using the picosecond pump-probe ionization TOF mass spectrometry and transient technique, are reported. The microcanonical nonradiative decay rate constants at the S1 manifold for trans-stilbene-hexanen and trans-stilbene-octanen (n = 1, 2) complexes, including certain deuterated variants, were measured as a function of excitation energy, with the energy range defined by tuning the pump wavelength from the 0-0 transition of trans-stilbene to ~3200 cm-1 higher in energy. The experimental results were modeled with standard RRKM theory, nonadiabatic RRKM theory and Kramers-type theory for microcanonical systems. It was found that the excess energy dependence results could be accounted for very well by the nonadiabatic RRKM theory, from which analysis the barriers to isomerization for all of the trans-stilbene n-alkane clusters were found to be lower than that of the parent molecule by ~50%. The analysis revealed that not only can the differences in the rates among the four trans-stilbene-hexane1 isotopic species studied (combinations of trans-stilbene-h12 and -d12 with n-hexane-h14 and -d14) be attributed to energy friction, a term describing how energy is \"drained away\" from the reaction coordinate as a result of the change in the vibrational density of states, but the reduction in the nonradiative rates of the 1:2 complexes, relative to that of the 1:1 complexes, can also be attributed to the same energy friction.
\r\n\r\nFinally, in the same studies, the cluster binding energies of trans-stilbene-hexanen and trans-stilbene-octanen were also determined.
", "date": "2001", "date_type": "degree", "id_number": "CaltechETD:etd-04072008-151825", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechETD:etd-04072008-151825", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "deposited_by": "Imported from ETD-db", "deposited_on": "2008-04-08", "doi": "10.7907/5m8y-hz17", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Zewail-A-H", "name": { "family": "Zewail", "given": "Ahmed H." }, "role": "advisor" }, { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "co-advisor" } ] }, "thesis_committee": { "items": [ { "id": "Okumura-M", "name": { "family": "Okumura", "given": "Mitchio" }, "orcid": "0000-0001-6874-1137", "role": "chair" }, { "id": "Barton-J-K", "name": { "family": "Barton", "given": "Jacqueline K." }, "orcid": "0000-0001-9883-1600", "role": "member" }, { "id": "McKoy-B-V", "name": { "family": "McKoy", "given": "Basil Vincent" }, "role": "member" }, { "id": "Zewail-A-H", "name": { "family": "Zewail", "given": "Ahmed H." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_submitted_date": "2008-04-07", "thesis_defense_date": "1999-08-09", "thesis_approved_date": "2008-04-08", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive\nlicense to archive and make accessible, under the conditions specified below,\nmy thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "2001", "author_list": "Chong, Sing Hwa", "advisor_list": "Zewail, Ahmed H. and Bercaw, John E.", "comittee_list": "Okumura, Mitchio; Barton, Jacqueline K.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/8181", "eprint_id": 8181, "rev_number": 21, "documents": [ { "id": "/id/document/47167", "doc_id": 47167, "rev_number": 3, "files": [ { "id": "/id/file/138026", "fileid": 138026, "datasetid": "document", "objectid": 47167, "filename": "Yoder_jc_2001.pdf", "mime_type": "application/pdf", "hash": "f969843f79298ce6e2b6feccc4d9e960", "hash_type": "MD5", "filesize": 36660534, "mtime": "2014-04-07 21:12:55", "url": "/8181/1/Yoder_jc_2001.pdf" } ], "eprint_id": 8181, "pos": 1, "placement": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", 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"/id/document/47167" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/47167" } ] } } ], "eprint_status": "archive", "userid": 87, "dir": "disk0/00/00/81/81", "datestamp": "2014-04-07 21:27:46", "lastmod": "2022-11-30 00:13:39", "status_changed": "2014-04-07 21:27:46", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Yoder-Jeffrey-Charles", "name": { "family": "Yoder", "given": "Jeffrey Charles" }, "show_email": "NO" } ] }, "title": "Model Studies of Ziegler-Natta Olefin Polymerization Using Group 3 and Group 4 Metallocenes", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "Evidence for the stereochemical isomerization of a variety of ansa\r\nmetallocene compounds is presented. For the scandocene allyl derivatives\r\ndescribed here, we have established that the process is promoted by a variety of\r\nsalts in both ether and hydrocarbon solvents and is not accelerated by light. A\r\nplausible mechanism based on an earlier proposal by Marks, et al., is offered as\r\nan explanation of this process. It involves coordination of anions and/or donor\r\nsolvents to the metal center with cation assistance to encourage metalcyclopentadienyl\r\nbond heterolysis, rotation about the Si-Cp bond of the\r\ndetached cyclopentadienide and recoordination of the opposite face. Our\r\nobservations in some cases of thermodynamic racemic:meso ratios under the\r\nreaction conditions commonly used for the synthesis of the metallocene\r\nchlorides suggests that the interchange is faster than metallation, such that the\r\ncomposition of the reaction mixture is determined by thermodynamic, not\r\nkinetic, control in these cases.
\r\n\r\nTwo new ansa-scandocene alkenyl compounds react with olefins resulting\r\nin the formation of \u03b73-allyl complexes. Kinetics and labeling experiments\r\nindicate a tuck-in intermediate on the reaction pathway; in this intermediate the\r\nmetal is bound to the carbon adjacent to the silyllinker in the rear of the\r\nmetallocene wedge. In contrast, reaction of permethylscandocene alkenyl\r\ncompounds with olefins results, almost exclusively, in vinylic C-H bond\r\nactivation. It is proposed that relieving transition state steric interactions\r\nbetween the cyclopentadienyl rings and the olefin by either linking the rings\r\ntogether or using a larger lanthanide metal may allow for olefin coordination,\r\nstabilizing the transition state for allylic \u03c3-bond metathesis.
\r\n\r\nA selectively isotopically labeled propylene, CH2CD(13CH3), was\r\nsynthesized and its polymerization was carried out at low concentration in\r\ntoluene solution using isospecific metallocene catalysts. Analysis of the NMR\r\nspectra (13C, 1H, and 2H) of the resultant polymers revealed that the production\r\nof stereoerrors through chain epimerization proceeds exclusively by the tertiaryalkyl\r\nmechanism. Additionally, enantiofacial inversion of the terminally\r\nunsaturated polymer chain occurs by a non-dissociative process. The\r\nimplications of these results on the mechanism of olefin polymerization with\r\nthese catalysts is discussed.
", "date": "2001", "date_type": "degree", "id_number": "CaltechTHESIS:04072014-140228693", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:04072014-140228693", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Tony Diaz", "deposited_by": "Benjamin Perez", "deposited_on": "2014-04-07 21:27:46", "doi": "10.7907/6qry-9x55", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." }, "role": "chair" }, { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" }, { "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "orcid": "0000-0002-0057-7817", "role": "member" }, { "id": "Tirrell-D-A", "name": { "family": "Tirrell", "given": "David A." }, "orcid": "0000-0003-3175-4596", "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "2000-06-08", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "2001", "author_list": "Yoder, Jeffrey Charles", "advisor_list": "Bercaw, John E.", "comittee_list": "Anson, Fred C.; Bercaw, John E.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/8161", "eprint_id": 8161, "rev_number": 19, "documents": [ { "id": "/id/document/46858", "doc_id": 46858, "rev_number": 3, "files": [ { "id": "/id/file/137390", "fileid": 137390, "datasetid": "document", "objectid": 46858, "filename": "Zubris_dl_2001.pdf", "mime_type": "application/pdf", "hash": "d29b80aef6019b0721c9ec1776f4cebb", "hash_type": "MD5", "filesize": 51236605, "mtime": "2014-03-24 23:07:56", "url": "/8161/1/Zubris_dl_2001.pdf" } ], "eprint_id": 8161, "pos": 1, "placement": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": 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"media_sample_stop": "0", "content": "final" }, { "id": "/id/document/128870", "doc_id": 128870, "rev_number": 1, "files": [ { "id": "/id/file/374306", "fileid": 374306, "datasetid": "document", "objectid": 128870, "filename": "indexcodes.txt", "mime_type": "text/plain", "hash": "dce9a1407696e8c9a550ede2d86f2a37", "hash_type": "MD5", "filesize": 30273, "mtime": "2021-06-24 03:17:25", "url": "/8161/8/indexcodes.txt" } ], "eprint_id": 8161, "pos": 8, "placement": 8, "mime_type": "text/plain", "format": "other", "format_desc": "Generate index codes conversion from application/pdf to indexcodes", "language": "en", "security": "public", "license": "other", "main": "indexcodes.txt", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/46858" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/46858" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/46858" } ] } } ], "eprint_status": "archive", "userid": 87, "dir": "disk0/00/00/81/61", "datestamp": "2014-03-25 16:34:50", "lastmod": "2022-11-30 00:39:41", "status_changed": "2014-03-25 16:34:50", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Zubris-Deanna-Lynn", "name": { "family": "Zubris", "given": "Deanna Lynn" }, "orcid": "0000-0003-1003-9630", "show_email": "NO" } ] }, "title": "Investigations of the Origin of Stereocontrol in Syndiospecific Ziegler-Natta Polymerizations", "ispublished": "unpub", "full_text_status": "public", "keywords": "Ziegler-Natta polymerizations ; Chemistry", "abstract": "In order to expand our understanding of the mechanism of stereocontrol\r\nin syndiospecific \u03b1-olefin polymerization, a family of Cs-symmetric, ansa-group 3\r\nmetallocenes was targeted as polymerization catalysts. The syntheses of new\r\nansa-yttrocene and scandocene derivatives that employ the doubly [SiMe2]-\r\nbridged ligand array (1,2-SiMe2)2{C5H-3,5-(CHMe2)2} (where R = t-\r\nbutyl, tBuThp; where R = i-propyl, iPrThp) are described. The structures of\r\ntBuThpY(\u00b5-Cl)2K(THF)2, tBuThpSc(\u00b5-Cl)2K(Et2O)2, tBuThpYCH(SiMe3)2, Y2{\u00b52-(tBuThp)2}(\u00b52-H)2, and tBuThpSc(\u00b5-CH3)2 have been examined by\r\nsingle crystal X-ray diffraction methods. Ansa-yttrocenes and scandocenes that\r\nincorporate the singly [CPh2]-bridged ligand array (CPh2)(C5H4)(C13H8)(where\r\nC5H4 = Cp, cyclopentadienyl; where C13H8 = Flu, fluourenyl) have also been\r\nprepared. Select meallocene alkyl complexes are active single component\r\ncatalysts for homopolymerization of propylene and 1-pentene. The scandocene\r\ntetramethylaluminate complexes generate polymers with the highes molecular\r\nweights of the series. Under all conditions examined atactic polymer\r\nmicrostructures are observed, suggesting a chain-end mechanism for\r\nstereocontrol.
\r\n\r\nA series of ansa-tantalocenes have been prepared as models for Ziegler-Natta\r\npolymerization catalysts. A singly bridged ansa-tantalocene trimethyl\r\ncomplex, Me2Si(\u03b75-C5H4)2TaMe3, has been prepared and used for the synthesis\r\nof a tantalocene ethylene-methyl complex. Addition of propylene to this\r\nethylene-methyl adduct results in olefin exchange to give a mixture of endo and\r\nexo propylene isomers. Doubly-silylene bridged ansa-tantalocene complexes\r\nhave been prepared with the tBuThp ligand; a tantalocene trimethyl complex and\r\na tantalocene methylidene-methyl complex have been synthesized and\r\ncharacterized by X-ray diffraction. Thermolysis of the methylidene-methyl\r\ncomplex affords the corresponding ethylene-hydride complex. Addition of\r\neither propylene or styrene to this ethylene-hydride compound results in olefin\r\nexchange. In both cases, only one product isomer is observed. Studies of olefin\r\nexchange with ansa-tantalocene olefin-hydride and olefin-methyl complexes have\r\nprovided information about the important steric influences for olefin\r\ncoordination in Ziegler-Natta polymerization.
\r\n\r\n", "date": "2001", "date_type": "degree", "id_number": "CaltechTHESIS:03242014-152154971", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:03242014-152154971", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "deposited_by": "Benjamin Perez", "deposited_on": "2014-03-25 16:34:50", "doi": "10.7907/j7gk-0s22", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "orcid": "0000-0002-0057-7817", "role": "chair" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876", "role": "member" }, { "id": "Rees-D-C", "name": { "family": "Rees", "given": "Douglas C." }, "orcid": "0000-0003-4073-1185", "role": "member" }, { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "2000-07-10", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "2001", "author_list": "Zubris, Deanna Lynn", "advisor_list": "Bercaw, John E.", "comittee_list": "Grubbs, Robert H.; Gray, Harry B.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/4490", "eprint_id": 4490, "rev_number": 13, "documents": [ { "id": "/id/document/7298", "doc_id": 7298, "rev_number": 4, "files": [ { "id": "/id/file/44524", "fileid": 44524, "datasetid": "document", "objectid": 7298, "filename": "Lai_r_2001.pdf", "mime_type": "application/pdf", "filesize": 4700896, "mtime": "2012-12-26 03:09:08", "url": "/4490/1/Lai_r_2001.pdf" } ], "eprint_id": 4490, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": "Lai_r_2001.pdf", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "final", "relation": { "items": [ { "type": "http://eprints.org/relation/hasVolatileVersion", "uri": "/id/document/23827" }, { "type": "http://eprints.org/relation/haspreviewThumbnailVersion", "uri": "/id/document/23827" }, { "type": "http://eprints.org/relation/hasVersion", "uri": "/id/document/23827" } ] } }, { "id": "/id/document/23827", "doc_id": 23827, "rev_number": 3, "files": [ { "id": "/id/file/44522", "fileid": 44522, "datasetid": "document", "objectid": 23827, "filename": "preview.png", "mime_type": "image/png", "hash": "41be3fcd02aa8a5642ad4845e2f74e50", "hash_type": "MD5", "filesize": 9990, "mtime": "2012-12-26 03:09:08", "url": "/4490/2/preview.png" } ], "eprint_id": 4490, "pos": 2, "placement": 2, "mime_type": "image/png", "format": "image/png", "language": "en", "security": "public", "license": "other", "main": "preview.png", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/7298" }, { "type": "http://eprints.org/relation/ispreviewThumbnailVersionOf", "uri": "/id/document/7298" }, { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/7298" } ] } }, { "id": "/id/document/124324", "doc_id": 124324, "rev_number": 1, "files": [ { "id": "/id/file/369754", "fileid": 369754, "datasetid": "document", "objectid": 124324, "filename": "indexcodes.txt", "mime_type": "text/plain", "hash": "897f3c69148b6b488d5b55c285be077a", "hash_type": "MD5", "filesize": 20733, "mtime": "2021-06-23 23:28:21", "url": "/4490/3/indexcodes.txt" } ], "eprint_id": 4490, "pos": 3, "placement": 3, "mime_type": "text/plain", "format": "other", "format_desc": "Generate index codes conversion from application/pdf to indexcodes", "language": "en", "security": "public", "license": "other", "main": "indexcodes.txt", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/7298" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/7298" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/7298" } ] } } ], "eprint_status": "archive", "userid": 2, "dir": "disk0/00/00/44/90", "datestamp": "2005-11-10", "lastmod": "2022-11-29 22:14:19", "status_changed": "2009-09-25 03:19:30", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Lai-Re", "name": { "family": "Lai", "given": "Re" }, "show_email": "NO" } ] }, "title": "Synthesis and Characterization of ZSM-5 Zeolite Membranes", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry and Chemical Engineering", "abstract": "Synthesis of ZSM-5 zeolite membranes supported on porous alumina substrates was conducted in autoclave reactors. The film morphologies and structures were characterized by scanning electron microscopy, energy dispersive spectroscopy and X-ray diffraction. Gas adsorption was used to estimate the crystalline fraction of the products. The gas permeation properties of the membranes were evaluated for H\u2082, CH\u2084, O\u2082, N\u2082, and n-butane and other gases singly or in mixtures.
\r\n\r\nZSM-5 film formation on alumina and other surfaces in certain clear, tetrapropylammonium(TPA\u207a)-containing synthesis solutions was found to be preceded by a gel layer. The presence of alumina and other substrates of a high Hamaker constant facilitated formation of the surface gel layer and accelerated zeolite crystallization. Aluminum added to the solution or leached from alumina substrates had dual effects, to induce surface gelation and to retard crystallization of that layer as well as crystallization in the bulk solution.
\r\n\r\nGrowth of ZSM-5 membranes was facilitated by using alumina tubes pre-coated with silicalite seeds. Accompanied with gradual growth of an external polycrystalline layer, siliceous deposits accumulated as deep as 100 \u00b5m inside the pores of the support, converting gradually from amorphous to crystalline. Pure gas permeation results are presented for membranes prepared in a solution of composition SiO\u2082: 0.15TPAB4: 0.7NaOH: 98H\u2082O using 0.4 and 2 \u00b5m seeds.
\r\n\r\nOrganic-free hydrogel reaction mixtures were further used to grow ZSM-5 membranes on seeded porous alumina substrates, eliminating the crack-prone calcination step for removing organic TPA\u207a templates from as-synthesized ZSM-5. The optimum composition SiO\u2082: 0.0125Al\u2082O\u2083: 0.2675Na\u2082O: 46H\u2082O was identified to produce membranes with permeation selectivities for H\u2082 over n-butane above 10\u2074 and for O\u2082 over N\u2082 9-10. The permeation was strongly activated with the activation energies increasing sharply with molecular size.
\r\n\r\nParallel synthesis of zeolite films was developed to expedite composition screening. The films prepared in an array reactor of multiple wells each containing 35 micro-liter synthesis solution displayed morphology similar to that produced by the conventional synthesis. The method was applied to explore the composition space of clear, organic-free synthesis solutions for ZSM-5 films growth: SiO\u2082: (700-300)Al\u2082O\u2083: (0.5-0.7)NaOH: 80H\u2082O.
", "date": "2001", "date_type": "degree", "id_number": "CaltechETD:etd-11102005-103556", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechETD:etd-11102005-103556", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "deposited_by": "Imported from ETD-db", "deposited_on": "2005-11-10", "doi": "10.7907/m5xs-mq20", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Gavalas-G-R", "name": { "family": "Gavalas", "given": "George R." }, "orcid": "0000-0003-1468-6835", "role": "advisor" }, { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "co-advisor" } ] }, "thesis_committee": { "items": [ { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." }, "role": "chair" }, { "id": "Davis-M-E", "name": { "family": "Davis", "given": "Mark E." }, "orcid": "0000-0001-8294-1477", "role": "member" }, { "id": "Gavalas-G-R", "name": { "family": "Gavalas", "given": "George R." }, "orcid": "0000-0003-1468-6835", "role": "member" }, { "id": "Okumura-M", "name": { "family": "Okumura", "given": "Mitchio" }, "orcid": "0000-0001-6874-1137", "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_submitted_date": "2005-11-10", "thesis_defense_date": "2000-07-24", "thesis_approved_date": "2005-11-10", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "option_minor": { "items": [ "chemeng" ] }, "copyright_statement": "I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive\nlicense to archive and make accessible, under the conditions specified below,\nmy thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "2001", "author_list": "Lai, Re", "advisor_list": "Gavalas, George R. and Bercaw, John E.", "comittee_list": "Anson, Fred C.; Davis, Mark E.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/8152", "eprint_id": 8152, "rev_number": 23, "documents": [ { "id": "/id/document/46780", "doc_id": 46780, "rev_number": 3, "files": [ { "id": "/id/file/137132", "fileid": 137132, "datasetid": "document", "objectid": 46780, "filename": "Rostovtsev 2001.pdf", "mime_type": "application/pdf", "hash": "9bed2ec953f0118b424d4bcadf6b7183", "hash_type": "MD5", "filesize": 26833972, "mtime": "2014-03-20 20:01:54", "url": "/8152/1/Rostovtsev 2001.pdf" } ], "eprint_id": 8152, "pos": 1, "placement": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", 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"media_sample_start": "0", "media_sample_stop": "0", "content": "final" }, { "id": "/id/document/128860", "doc_id": 128860, "rev_number": 1, "files": [ { "id": "/id/file/374296", "fileid": 374296, "datasetid": "document", "objectid": 128860, "filename": "indexcodes.txt", "mime_type": "text/plain", "hash": "9493a3bdb8434147656e2b0fe27dd596", "hash_type": "MD5", "filesize": 36272, "mtime": "2021-06-24 03:16:22", "url": "/8152/8/indexcodes.txt" } ], "eprint_id": 8152, "pos": 8, "placement": 8, "mime_type": "text/plain", "format": "other", "format_desc": "Generate index codes conversion from application/pdf to indexcodes", "language": "en", "security": "public", "license": "other", "main": "indexcodes.txt", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/46780" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/46780" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/46780" } ] } } ], "eprint_status": "archive", "userid": 50, "dir": "disk0/00/00/81/52", "datestamp": "2014-03-20 20:38:40", "lastmod": "2022-11-29 23:19:05", "status_changed": "2014-03-20 20:38:40", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Rostovtsev-Vsevolod-Vladimirovich", "name": { "family": "Rostovtsev", "given": "Vsevolod Vladimirovich" }, "orcid": "0000-0002-1226-5909", "show_email": "NO" } ] }, "title": "Reactions of Platinum(II) Complexes with Dioxygen: Progress Toward Alkane Functionalization", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "Whereas stoichiometric activation of C-H bonds by complexes of transition metals is\r\nbecoming increasingly common, selective functionalization of alkanes remains a\r\nformidable challenge in organometallic chemistry. The recent advances in catalytic\r\nalkane functionalization by transition-metal complexes are summarized in Chapter I.
\r\n\r\nThe studies of the displacement of pentafluoropyridine in\r\n[(tmeda)Pt(CH_3)(NC_5F_5)][BAr^f_4] (1) with \u03b3- tetrafluoropicoline, a very poor nucleophile,\r\nare reported in Chapter II. The ligand substitution occurs by a dissociative interchange\r\nmechanism. This result implies that dissociative loss of pentafluoropyridine is the rate-limiting\r\nstep in the C-H activation reactions of 1.
\r\n\r\nOxidation of dimethylplatinum(II) complexes (N-N)Pt(CH_3)_2 (N-N = tmeda(1), \u03b1-diimines)\r\nby dioxygen is described in Chapter III. Mechanistic studies suggest a two-step mechanism. First, a hydroperoxoplatinum(IV) complex is formed in a reaction\r\nbetween (N-N)Pt(CH_3)_2 and dioxygen. Next, the hydroperoxy complex reacts with a\r\nsecond equivalent of (N-N)Pt(CH_3)_2 to afford the final product,\r\n(N-N)Pt(OH)(OCH_3)(CH_3)_2. The hydroperoxy intermediate,\r\n(tmeda)Pt(OOH)(OCH_3)(CH_3)_2 (2), was isolated and characterized. The reactivity of 2\r\nwith several dime thylplatinum(II) complexes is reported.
\r\n\r\nThe studies described in Chapter IV are directed toward the development of a\r\nplatinum(II)-catalyzed oxidative alkane dehydrogenation. Stoichiometric conversion of\r\nalkanes (cyclohexane, ethane) to olefins (cyclohexene, ethylene) is achieved by C-H\r\nactivation with [(N-N)Pt(CH_3)(CF_3CH_2OH)]BF_4 (1, N-N is N,N'-bis(3,5-di-t-\r\nbutylphenyl)-1,4-diazabutadiene) which results in the formation of olefin hydride\r\ncomplexes. The first step in the C-H activation reaction is formation of a platinum(II)\r\nalkyl which undergoes \u03b2-hydrogen elimination to afford the olefin hydride complex.\r\nThe cationic ethylplatinum(II) intermediate can be generated in situ by treating\r\ndiethylplatinum(II) compounds with acids. Treatment of (phen)PtEt_2 with\r\n[H(OEt_2)_2]Bar^f_4 at low temperatures resulted in the formation of a mixture of\r\n[(phen)PtEt(OEt_2)]Bar^f_4 (8) and [(phen)Pt(C_2H_4)H] Bar^f_4 (7). The cationic olefin\r\ncomplexes are unreactive toward dioxygen or hydrogen peroxide. Since the success of\r\nthe overall catalytic cycle depends on our ability to oxidize the olefin hydride\r\ncomplexes, a series of neutral olefin complexes of platinum(II) with monoanionic ligands\r\n(derivatives of pyrrole-2-carboxyaldehyde N-aryl imines) was prepared. Unfortunately,\r\nthese are also stable to oxidation.
\r\n", "date": "2001", "date_type": "degree", "id_number": "CaltechTHESIS:03202014-115036901", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:03202014-115036901", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Tony Diaz", "deposited_on": "2014-03-20 20:38:40", "doi": "10.7907/jevj-7928", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876", "role": "chair" }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." }, "role": "member" }, { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" }, { "id": "Labinger-J-A", "name": { "family": "Labinger", "given": "Jay A." }, "orcid": "0000-0002-1942-9232", "role": "member" }, { "id": "Stoltz-B-M", "name": { "family": "Stoltz", "given": "Brian M." }, "orcid": "0000-0001-9837-1528" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "2001-05-29", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "2001", "author_list": "Rostovtsev, Vsevolod Vladimirovich", "advisor_list": "Bercaw, John E.", "comittee_list": "Gray, Harry B.; Anson, Fred C.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/1843", "eprint_id": 1843, "rev_number": 8, "documents": [ { "id": "/id/document/3072", "doc_id": 3072, "rev_number": 3, "files": [ { "id": "/id/file/18487", "fileid": 18487, "datasetid": "document", "objectid": 3072, "filename": "Thesis.pdf", "mime_type": "application/pdf", "filesize": 3788034, "mtime": "2012-12-26 02:42:55", "url": "/1843/1/Thesis.pdf" } ], "eprint_id": 1843, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "format_desc": "Thesis.pdf", "language": "en", "security": "public", "license": "other", "main": "Thesis.pdf", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "final", "relation": { "items": [ { "type": "http://eprints.org/relation/hasVolatileVersion", "uri": "/id/document/19773" }, { "type": "http://eprints.org/relation/haspreviewThumbnailVersion", "uri": "/id/document/19773" }, { "type": "http://eprints.org/relation/hasVersion", "uri": "/id/document/19773" } ] } }, { "id": "/id/document/19773", "doc_id": 19773, "rev_number": 3, "files": [ { "id": "/id/file/18485", "fileid": 18485, "datasetid": "document", "objectid": 19773, "filename": "preview.png", "mime_type": "image/png", "hash": "4dc57feb8ad17c43c7f0adf95e0af07b", "hash_type": "MD5", "filesize": 13321, "mtime": "2012-12-26 02:42:55", "url": "/1843/2/preview.png" } ], "eprint_id": 1843, "pos": 2, "placement": 2, "mime_type": "image/png", "format": "image/png", "language": "en", "security": "public", "license": "other", "main": "preview.png", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/3072" }, { "type": "http://eprints.org/relation/ispreviewThumbnailVersionOf", "uri": "/id/document/3072" }, { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/3072" } ] } }, { "id": "/id/document/121372", "doc_id": 121372, "rev_number": 1, "files": [ { "id": "/id/file/366764", "fileid": 366764, "datasetid": "document", "objectid": 121372, "filename": "indexcodes.txt", "mime_type": "text/plain", "hash": "7bcf0539bd013df72623df477e146bf1", "hash_type": "MD5", "filesize": 41590, "mtime": "2021-06-23 21:25:01", "url": "/1843/3/indexcodes.txt" } ], "eprint_id": 1843, "pos": 3, "placement": 3, "mime_type": "text/plain", "format": "other", "format_desc": "Generate index codes conversion from application/pdf to indexcodes", "language": "en", "security": "public", "license": "other", "main": "indexcodes.txt", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/3072" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/3072" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/3072" } ] } } ], "eprint_status": "archive", "userid": 2, "dir": "disk0/00/00/18/43", "datestamp": "2004-05-19", "lastmod": "2021-04-16 23:25:37", "status_changed": "2009-09-25 02:17:27", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "samiller@mail.chem.tamu.edu", "id": "Miller-S-A", "name": { "family": "Miller", "given": "Stephen Albert" }, "show_email": "YES" } ] }, "title": "Metallocene-mediated olefin polymerization : the effects of distal ligand perturbations on polymer stereochemistry", "ispublished": "unpub", "full_text_status": "public", "keywords": "metallocene; polymerization; polypropylene", "abstract": "New group IV compounds containing a 9-dialkylaminofluorenide ligand have been prepared. Their properties and reactivity have been investigated. For example, single crystal X-ray analysis of the metallocene (9-(N,N-dimethylamino)fluorenyl)2ZrCl2 (4) reveals a bonding mode that includes a zirconium-nitrogen bond. In combination with methylaluminoxane (MAO), several aminofluorenide complexes afford atactic polypropylene.\n\nA statistical model has been developed that quantifies the unidirectional site epimerization probability, e, for singly- and doubly-bridged C1- symmetric metallocene polymerization catalysts. The unidirectional site epimerization model allows deconvolution of the site sequence probability and the stereochemical probability for producing a given pentad.\n\nHighly stereoregular syndiotactic polypropylene is obtained with the catalyst systems Ph2C(Oct)(C5H4)ZrCl2/MAO (8/MAO) (Oct = octamethyloctahydrodibenzofluorenyl, C-29H36) and Me2C(Oct)(C5H4)ZrCl2/MAO (12/MAO). Melting temperatures as high as 153?C or 154?C are found for the thermally quenched polymers. Distal ligand perturbations are demonstrated to have a dramatic effect on polymer stereochemistry.\n\nPolypropylenes that are isotactic-hemiisotactic or syndiotactic-hemiisotactic can be made with proper R substituent selection in the catalyst system Me2C(Flu)(3-R-C5H3)ZrCl2/MAO or Me2C(Oct)(3-R-C5H3)ZrCl2/MAO, where Flu = fluorenyl (C13H8). The prepared polymers have been subjected to a statistical model which suggests that the metallocenes have one highly selective site (99%) and one site of variable selectivity which is highly dependent on the nature of the R substituent and whether the metallocene contains the Flu or Oct ligand.\n\nControl of the tacticity of isotactic-hemiisotactic polypropylene, as quantified by the parameter a, is achieved by proper R substituent selection in the catalyst system R'2C(3-R-C5H3)(C13H8)MCl2/MAO. For R = 2-adamantyl, R' = Ph, and M = Zr or Hf, a is approximately 0.60 and the polypropylene obtained is elastomeric. Its properties are rationalized by the statistical existence of isotactic stereoblocks among an otherwise amorphous hemiisotactic medium.\n\nFor the C1-symmetric polymerization catalyst Me2C(3-t-butyl-C5H3)(9-C13H8)ZrCl2/MAO, evidence gathered here supports an alternating mechanism in which both sites of the metallocene wedge are utilized for monomer insertion. For an Oct-containing catalyst system with a cyclopentadienyl substituent of R = 2-methyl-2-adamantyl, unprecedentedly high isotacticity (>99% [mmmm]) is observed for a fluorenyl-based metallocene catalyst. Melting temperatures for such isotactic polymers can be as high as 167?C (Tp = 0?C).", "date": "2000", "date_type": "degree", "id_number": "CaltechETD:etd-05172004-054229", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechETD:etd-05172004-054229", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "deposited_by": "Imported from ETD-db", "deposited_on": "2004-05-19", "doi": "10.7907/51r0-km07", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "id": "Goddard-W-A-III", "name": { "family": "Goddard", "given": "William A., III" }, "role": "chair" }, { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" }, { "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan Saul" }, "role": "member" }, { "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_submitted_date": "2004-05-17", "thesis_defense_date": "1999-11-30", "thesis_approved_date": "2004-05-19", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive\nlicense to archive and make accessible, under the conditions specified below,\nmy thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "2000", "author_list": "Miller, Stephen Albert", "advisor_list": "Bercaw, John E.", "comittee_list": "Goddard, William A., III; Bercaw, John E.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/10841", "eprint_id": 10841, "rev_number": 20, "documents": [ { "id": "/id/document/88098", "doc_id": 88098, "rev_number": 4, "files": [ { "id": "/id/file/250028", "fileid": 250028, "datasetid": "document", "objectid": 88098, "filename": "STAHL_SS_1997.pdf", "mime_type": "application/pdf", "hash": "d75a63f4d867e318dcb97a5e490ee3ee", "hash_type": "MD5", "filesize": 50839058, "mtime": "2018-05-01 17:04:56", "url": "/10841/1/STAHL_SS_1997.pdf" } ], "eprint_id": 10841, "pos": 1, "placement": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": 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"/id/document/88098" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/88098" } ] } } ], "eprint_status": "archive", "userid": 1660, "dir": "disk0/00/01/08/41", "datestamp": "2018-05-01 18:20:10", "lastmod": "2020-12-02 02:34:55", "status_changed": "2018-05-01 18:20:10", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "stahl@chem.wisc.edu", "id": "Stahl-Shannon-Scot", "name": { "family": "Stahl", "given": "Shannon Scot" }, "orcid": "0000-0002-9000-7665", "show_email": "NO" } ] }, "title": "Mechanistic Studies of Alkane Activation by Platinum(II) Complexes", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "Currently, there is considerable interest in alkane oxidation reactions catalyzed by transition metal complexes. Chapter 1 reviews many of the recent advances in this field involving electrophilic late transition metals. The C-H activation step appears to dictate both the rate and selectivity of these reactions. Unfortunately, however, very little is known about the mechanism of this step.
\r\n\r\nIn chapter 2, mechanistic studies of the protonolysis of several alkylplatinum(II) complexes [(tmeda)PtMeCl, (tmeda)Pt(CH2Ph)Cl, (tmeda)PtMe2, and trans(PEt3)2Pt(CH3)Cl] are described. These reactions model the microscopic reverse of C-H activation by aqueous Pt(II). Kinetics, activation parameters, and isotope effects were determined, and the results support a common mechanistic sequence for all of the reactions: (1) chloride- or solvent-mediated protonation of Pt(II) to generate an alkylhydridoplatinum(IV) intermediate, (2) dissociation of solvent or chloride to generate a cationic, five-coordinate platinum(IV) species, (3) reductive C-H bond formation producing a platinum(II) alkane \u03c3-complex, and (4) loss of alkane either through an associative or dissociative substitution pathway. These studies provide insight into the role of solvent and ancillary ligands in aqueous Pt(II)-mediated C-H activation. The results also support the viability of Pt(II) \u03c3-adducts and alkylhydridoplatinum(IV) intermediates in this reaction.
\r\n\r\nChapter 3 describes the preparation and study of Pt(II) H2-adducts and Pt(IV) dihydride complexes. The species of interest are generated by protonation of hydridoplatinum(II) complexes of the type trans-(PCy3)2Pt(H)X [X = SiH3, H, CH3, Ph, Cl, Br, I, CN, CF3SO3] and [trans-(PCy3)2Pt(H)L][Barf4] [L = CO, 4-picoline; Barf4] = B(3,5-C6H3(CF3)2)4]. The proton attacks one of three different sites on these complexes (hydride, platinum, or the trans ligand), depending on which ligand is trans to hydride. These studies reveal several factors affecting the stability and reactivity of Pt(II) \u03c3-adducts, which thus have implications for C-H activation by Pt(II).
\r\n", "date": "1997", "date_type": "degree", "id_number": "CaltechTHESIS:05012018-081029790", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:05012018-081029790", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "deposited_by": "Bianca Rios", "deposited_on": "2018-05-01 18:20:10", "doi": "10.7907/CCAZ-9234", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "chair" }, { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" }, { "id": "Carreira-E-M", "name": { "family": "Carreira", "given": "Erick Moran" }, "role": "member" }, { "id": "Labinger-J-A", "name": { "family": "Labinger", "given": "Jay A." }, "role": "member" }, { "id": "Myers-A-G", "name": { "family": "Myers", "given": "Andrew G." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1997-05-19", "thesis_awards": "The Herbert Newby McCoy Award, 1997.", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1997", "author_list": "Stahl, Shannon Scot", "advisor_list": "Bercaw, John E.", "comittee_list": "Gray, Harry B.; Bercaw, John E.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/13583", "eprint_id": 13583, "rev_number": 13, "documents": [ { "id": "/id/document/104676", "doc_id": 104676, "rev_number": 3, "files": [ { "id": "/id/file/314823", "fileid": 314823, "datasetid": "document", "objectid": 104676, "filename": "kiely-af-1997.pdf", "mime_type": "application/pdf", "hash": "09ece36e5a4ab2ef2d12460dd9ad24dd", "hash_type": "MD5", "filesize": 7295180, "mtime": "2019-11-20 23:50:36", "url": "/13583/1/kiely-af-1997.pdf" } ], "eprint_id": 13583, "pos": 1, "placement": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": 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oxidation resistant ligand for ruthenium chemistry. The silver salt of tricyclophosphate, Ag\u2083(P\u2083O\u2089).H\u2082O, was found to be a useful synthon in the preparation of organic soluble tricyclophosphate salts. The complex [(P\u2083O\u2089)Ru(C\u2086H\u2086)]\u207b was prepared and characterized. In water, it was found that the tricyclophosphate ligand dissociated from the [(C\u2086H\u2086)Ru]\u00b2\u207a dication. Cyclic voltammatry in acetonitrile shows only a small irreversible oxidation at 0.95 V (Vs ferrocene). The rhenium carbonyl complex [(P\u2083O\u2089)Re(C0)\u2083]\u00b2\u207b was also investigated as a precursor to high valent tricyclophosphate rhenium complexes. Based on these results as well as related work by Klemperer and coworkers, it is concluded that the tricyclophosphate ligand is an exceptionally hard one that binds only weakly to transition metals.
\r\n\r\nThe preparations of chloro and allyl derivatives of pentamethylcyclopentadienyl aminoborole hafnium complexes are described. The chloro derivative, Cp*[C\u2084H\u2084BN(CHMe\u2082)\u2082]HfCl\u2022LiCl, is prepared by treatment of Cp*HfCl\u2083 with Li\u2082(THF){C\u2084H\u2084BN(CHMe\u2082)\u2082}. The structures of the chloro derivatives Cp*[C\u2084H\u2084BN(CHMe\u2082)\u2082]HfCl\u2022LiCl(Et\u2082O)\u2082 and {Cp*[C\u2084H\u2084BN(CHMe\u2082)\u2082]HfCl-LiCl}\u2082 were determined by single crystal X-ray analysis. Treatment of Cp*[C\u2084H\u2084BN(CHMe\u2082)\u2082]HfCl\u2022LiCl with allyl magnesium bromide yields Cp*[C\u2084H\u2084BN(CHMe\u2082)\u2082]Hf(\u03b7\u00b3-C\u2083H\u2085), whose structure was determined by X-ray analysis. The allyl species was active for the polymerization of ethylene, but not for the polymerization of \u03b1-olefins. Addition of ligands to the allyl derivative results in the formation of Cp*[C\u2084H\u2084BN(CHMe\u2082)\u2082]Hf(C\u2083H\u2085)(L) (L = PMe\u2083, pyridine, CO). The structure of Cp*[C\u2084H\u2084BN(CHMe\u2082)\u2082]Hf(\u03b7\u00b3-C\u2083H\u2085)(CO) was determined. Treatment of Cp*[C\u2084H\u2084BN(CHMe\u2082)\u2082]Hf(\u03b7\u00b3-C\u2083H\u2085)(CO) with PMe\u2083 results in the formation of the dieneolate complex Cp*[C\u2084H\u2084BN(CHMe\u2082)\u2082]Hf(OCHCHCHCH\u2082) (PMe\u2083). The electronic spectra of several aminoborole complexes were investigated and the low energy transitions assigned as borole-metal LMCT transitions. The amphoteric complex Cp*{\u03b7\u2075-C\u2084H\u2084BN(CHMe\u2082)\u2082}HfCl\u2022LiCl heterolytically cleaves H-X bonds to form Cp*{\u03b7\u2075-C\u2084H\u2084BNH(CHMe\u2082)\u2082}HfCl(X) (X = Cl, CCR). Cp*{\u03b7\u2075-C\u2084H\u2084BNH(CHMe\u2082)\u2082}Hf(CCTMS)\u2082 is prepared from Cp*{\u03b7\u2075-C\u2084H\u2084BN(CHMe\u2082)\u2082}Hf(\u03b7\u00b3-C\u2083H\u2085) and two equivalents of (trimethylsilyl)acetylene. Methyl iodide reacts with Cp{\u03b7\u2075-C\u2084H\u2084BN(CHMe\u2082)\u2082}HfCl\u2022LiCl to form Cp*{\u03b7\u2075-C\u2084H\u2083MeBNH(CHMe\u2082)\u2082}HfClI. Control experiments using deuterium labelled substrates show heterolysis occurs with no incorporation of deuterium into the 2,5 positions of the borole heterocycle. The X-ray structure determinations of Cp*{\u03b7\u2075-C\u2084H\u2084BNH(CHMe\u2082)\u2082}HfCl\u2082, Cp*{\u03b7\u2075-C\u2084H\u2084BNH(CHMe\u2082)\u2082}HfCl(CCTMS), and Cp*{\u03b7\u2075-C\u2084H\u2083MeBN(CHMe\u2082)\u2082}HfClI are reported.
", "date": "1997", "date_type": "degree", "id_number": "CaltechTHESIS:11202019-140851898", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:11202019-140851898", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Melissa Ray", "other_numbering_system": { "items": [ { "id": "9704397", "name": "UMI" } ] }, "deposited_by": "Mel Ray", "deposited_on": "2019-11-20 23:52:21", "doi": "10.7907/n5nr-dx22", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "chair" }, { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" }, { "email": "dadougherty@caltech.edu", "id": "Dougherty-D-A", "name": { "family": "Dougherty", "given": "Dennis A." }, "role": "member" }, { "email": "nslewis@its.caltech.edu", "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan Saul" }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1996-08-20", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1997", "author_list": "Kiely, Andrew F.", "advisor_list": "Bercaw, John E.", "comittee_list": "Gray, Harry B.; Bercaw, John E.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/13580", "eprint_id": 13580, "rev_number": 18, "documents": [ { "id": "/id/document/104616", "doc_id": 104616, "rev_number": 3, "files": [ { "id": "/id/file/314585", "fileid": 314585, "datasetid": "document", "objectid": 104616, "filename": "herzog-ta-1997.pdf", "mime_type": "application/pdf", "hash": "2d7c02b5cdb2a91ae21da86298e2f373", "hash_type": "MD5", "filesize": 8743116, "mtime": "2019-11-20 02:02:15", "url": "/13580/1/herzog-ta-1997.pdf" } ], "eprint_id": 13580, "pos": 1, "placement": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": 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"0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/104616" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/104616" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/104616" } ] } } ], "eprint_status": "archive", "userid": 8820, "dir": "disk0/00/01/35/80", "datestamp": "2019-11-20 02:09:44", "lastmod": "2021-04-16 23:31:26", "status_changed": "2019-11-20 02:09:44", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Herzog-Timothy-Allan", "name": { "family": "Herzog", "given": "Timothy Allan" }, "show_email": "NO" } ] }, "title": "Deuterium Isotope Effects as Evidence for \u03b1-Agostic Assistance in Ziegler-Natta Catalysts. Design, Synthesis, and Reactivity of a New Class of Highly Syndiospecific Ziegler-Natta Polymerization Catalysts", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "note": "The thesis title listed in 1997 commencement program -- Deuterium Isotope Effects as Evidence for \u03b1-Agostic Assistance in Ziegler-Natta Catalysts. Design, Synthesis, and Reactivity of a New Class of Highly Syndiospecific, Ziegler-Natta, Olefin Polymerization Catalysts -- varies from the actual thesis title.", "abstract": "By applying the concept of \"isotopic perturbation of stereochemistry\" to a number of Group III metallocene catalysts, further evidence for an \u03b1-agostic interaction in the chain propagation step of Ziegler-Natta polymerization has been obtained. These results are in accord with the \"modified Green-Rooney\" mechanism. An \u03b1-agostic interaction in the transition state of olefin insertion may contribute to the remarkable stereoselectivities of many Ziegler-Natta catalyst systems since it may restrict the possible orientations of the polymer chain such that it has a more significant impact on the orientation of the inserting olefin.
\r\n\r\nA new class of Group IV metallocene catalysts is presented for the syndiospedfic polymerization of propylene. These catalysts incorporate what are thought to be the key characteristics of syndiospedfic metallocene catalysts: Cs symmetry and rigidly linked cyclopentadienyls of greatly differing size. However, preliminary attempts to develop new syndioselective catalysts have suggested another important characteristic: a pocket in the larger moiety to avoid undesirable steric interactions between the ligand framework and coordinated olefin. In order to accommodate this constraint, a ligand system with a 1,3-dialkylcyclopentadienyl doubly linked to a singly substititued cydopentadienyl was chosen. Group IV metallocenes with these new ligands, in the presence of a cocatalyst (MAO), react rapidly with neat propylene to form highly syndiotactic polypropylene. This is the first example of a stereospecific doubly bridged olefin polymerization catalyst and is the first example of a highly syndiospedfic polymerization catalyst not based on a fluorenyl like ligand. This catalyst system is also very versatile since straightforward changes in the alkyl group of the singly substituted cydopentadienyl and in the reaction conditions lead to dramatic changes in the polymer microstructure. These catalysts should provide an excellent platform for mechanistic study and may be important industrially.
", "date": "1997", "date_type": "degree", "id_number": "CaltechTHESIS:11192019-173846004", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:11192019-173846004", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Melissa Ray", "other_numbering_system": { "items": [ { "id": "9704395", "name": "UMI" } ] }, "deposited_by": "Mel Ray", "deposited_on": "2019-11-20 02:09:44", "doi": "10.7907/tv4y-w681", "alt_title": { "items": [ "Deuterium Isotope Effects as Evidence for \u03b1-Agostic Assistance in Ziegler-Natta Catalysts", "Design, Synthesis, and Reactivity of a New Class of Highly Syndiospecific, Ziegler-Natta, Olefin Polymerization Catalysts" ] }, "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "rhg@caltech.edu", "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "role": "chair" }, { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" }, { "email": "wag@caltech.edu", "id": "Goddard-W-A-III", "name": { "family": "Goddard", "given": "William A., III" }, "role": "member" }, { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1996-06-17", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1997", "author_list": "Herzog, Timothy Allan", "advisor_list": "Bercaw, John E.", "comittee_list": "Grubbs, Robert H.; Bercaw, John E.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/11894", "eprint_id": 11894, "rev_number": 20, "documents": [ { "id": "/id/document/104372", "doc_id": 104372, "rev_number": 3, "files": [ { "id": "/id/file/313552", "fileid": 313552, "datasetid": "document", "objectid": 104372, "filename": "Blake_RE_1996.pdf", "mime_type": "application/pdf", "hash": "9961fc1ed4e8e5c36f48d0866ada19bc", "hash_type": "MD5", "filesize": 43955318, "mtime": "2019-11-11 23:31:55", "url": "/11894/1/Blake_RE_1996.pdf" } ], "eprint_id": 11894, "pos": 1, "placement": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", 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"http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/104372" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/104372" } ] } } ], "eprint_status": "archive", "userid": 8820, "dir": "disk0/00/01/18/94", "datestamp": "2019-11-05 20:01:55", "lastmod": "2021-04-16 22:55:17", "status_changed": "2019-11-05 20:01:55", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Blake-Robert-Edward-Jr", "name": { "family": "Blake", "given": "Robert Edward, Jr." }, "show_email": "NO" } ] }, "title": "The Synthesis, Characterization and Study of Transition Metal Complexes for the Oxidation and Activation of Hydrocarbons", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "The reaction of previously characterized ruthenium oxo complex, [LOEtRuV(O)(\u00b5-O)]2 with alcohol substrates was undertaken to elucidate the mechanism of the oxidation reaction. Unfortunately, an autocatalytic reaction between the organometallic product, [LOEtRuIV(OH)(\u00b5-O)]2 and the reactant alcohol, as well as catalyst decomposition made exact determinations of rate constants impossible. During the course of this investigation, the free acid form of the ligand, LOEtH, was isolated as a viscous oil. Subsequent investigation of the reactions of [LOEtRuV(O)(\u00b5-O)]2 with other species such as acids, salts and bases demonstrated the inherent instability of the complex. In several cases, initial products were spectroscopically characterized, but isolation of pure compounds was not achieved.
\r\n\r\nGiven the problems with the decomposition of ruthenium complexes which utilized the Klaui ligand, trimetaphosphate was studied as a potentially oxidation-resistant alternative for the development of oxidation catalysts. Attempts were made to prepare salts of the trimetaphosphate ligand which are soluble in nonpolar media and free of water of hydration. Coordination complexes of the trimetaphosphate anion and transition elements were synthesized. The mode of coordination and stability of the ligand was examined by infrared and visible spectroscopy. In all cases, the very weakly coordinating trimetaphosphate anion failed to displace other weakly associated ligands from the metal, failed to adopt the proper coordination geometry or was easily removed from the metal center by water.
\r\n\r\nHexabenzyloxycyclotriphosphatriene was synthesized and thermally rearranged to 1,3,5 - tribenzyl - 2,4,6 tribenzyloxy - 2,4,6 trioxocyclotriphosphazane as per published procedures. Characterization of the rearranged product by NMR techniques revealed the previously undetermined stereochemistry of the product. This ligand precursor has been shown to react with trialkyl silyl chlorides, although the products have not been characterized.
\r\n\r\nCp*2Ta(=NtBu)(THF)[B(C6F5)4] (1) was synthesized according to the method developed previously in our group. A cationic analog to Bergman's Cp2Zr(=NtBu), the reactivity of this complex to hydrocarbon substrates was studied. Contrary to previous reports, this complex does not react with methane, but C-H activation reactions were observed for propyne and phenyl acetylene. In the propyne case, an initial mixture of the [2+2] and C-H activation products was driven to exclusively the C-H activation product thermally. An interesting intramolecular activation of a Cp* methyl group precludes much of the desired C-H activation chemistry. The steric demands of the active site was demonstrated by the observed reaction with ethylene, but the lack of reactivity towards propene. A very interesting dealkylation of the imido group was observed upon reaction with carbon dioxide, which is proposed to involve the intermediacy of a coordinated isocyanate. Cp*2Ta(=NtBu)(THF)[B(C6F5)4] reacts as expected with water, HCl and dihydrogen, and reacts cleanly with methylene chloride to give Cp*2Ta(NHtBu)Cl[B(C6F5)4]. Many of the new compounds have been crystallographically and spectroscopically characterized. The reactivity of this complex can be rationalized in terms of the presence of both electrophilic and nucleophilic sites in the same molecule.
", "date": "1996", "date_type": "degree", "id_number": "CaltechTHESIS:11052019-113518368", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:11052019-113518368", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" } ] }, "collection": "CaltechTHESIS", "reviewer": "Melissa Ray", "deposited_by": "Mel Ray", "deposited_on": "2019-11-05 20:01:55", "doi": "10.7907/s731-np77", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "wag@caltech.edu", "id": "Goddard-W-A-III", "name": { "family": "Goddard", "given": "William A., III" }, "role": "chair" }, { "email": "fanson@caltech.edu", "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." }, "role": "member" }, { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" }, { "email": "jlbchamp@caltech.edu", "id": "Beauchamp-J-L", "name": { "family": "Beauchamp", "given": "Jesse L." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1995-07-27", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1996", "author_list": "Blake, Robert Edward, Jr.", "advisor_list": "Bercaw, John E.", "comittee_list": "Goddard, William A., III; Anson, Fred C.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/3936", "eprint_id": 3936, "rev_number": 8, "documents": [ { "id": "/id/document/6590", "doc_id": 6590, "rev_number": 3, "files": [ { "id": "/id/file/39749", "fileid": 39749, "datasetid": "document", "objectid": 6590, "filename": "Hajela_s_1995.pdf", "mime_type": "application/pdf", "filesize": 4764585, "mtime": "2012-12-26 03:04:07", "url": "/3936/1/Hajela_s_1995.pdf" } ], "eprint_id": 3936, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "format_desc": "Hajela_s_1995.pdf", "language": "en", "security": "public", "license": "other", "main": "Hajela_s_1995.pdf", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "final", "relation": { "items": [ { "type": "http://eprints.org/relation/hasVolatileVersion", "uri": "/id/document/23122" }, { "type": "http://eprints.org/relation/haspreviewThumbnailVersion", "uri": "/id/document/23122" }, { "type": "http://eprints.org/relation/hasVersion", "uri": "/id/document/23122" } ] } }, { "id": "/id/document/23122", "doc_id": 23122, "rev_number": 3, "files": [ { "id": "/id/file/39747", "fileid": 39747, "datasetid": "document", "objectid": 23122, "filename": "preview.png", "mime_type": "image/png", "hash": "b7fdb3d300f4b8147aee81b91b0359db", "hash_type": "MD5", "filesize": 12116, "mtime": "2012-12-26 03:04:07", "url": "/3936/2/preview.png" } ], "eprint_id": 3936, "pos": 2, "placement": 2, "mime_type": "image/png", "format": "image/png", "language": "en", "security": "public", "license": "other", "main": "preview.png", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/6590" }, { "type": "http://eprints.org/relation/ispreviewThumbnailVersionOf", "uri": "/id/document/6590" }, { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/6590" } ] } } ], "eprint_status": "archive", "userid": 2, "dir": "disk0/00/00/39/36", "datestamp": "2007-10-19", "lastmod": "2021-04-16 23:13:18", "status_changed": "2009-09-25 03:08:14", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Hajela-S", "name": { "family": "Hajela", "given": "Sharad" }, "show_email": "NO" } ] }, "title": "Synthetic, structural, and mechanistic studies of homogeneous Ziegler-Natta catalysis", "ispublished": "unpub", "full_text_status": "public", "abstract": "NOTE: Text or symbols not renderable in plain ASCII are indicated by [...]. Abstract is included in .pdf document.\n\nThe reaction of [...] with isobutene produces [...] along with isobutane, 2-methylpentane, isobutene, 2-methyl-l-pentene, propane and n-pentane. These products arise from a series of reactions involving olefin insertion, [...] and (faster) [...] elimination which proceeds until only the 2-methyl-l-alkenes [...] and the predominant organoscandium product [...] remain. A transient observed in the reaction sequence has been characterized as [...]. Slower [...] bond metathesis involving the methyl C-H bonds of [...] and the Sc-C bonds of the scandium alkyls accounts for the observation of saturated alkanes (2-methylalkanes [...], etc. ), normal alkanes [...] as well as a minor organoscandium product [...] in the product mixture. [...]-Ethyl migration is not observed for the closely related 2-ethyl-butyl derivative, [...], obtained from reaction of 2-ethyl-1-butene with [...].\n\nThe cyclopentylmethyl derivative, [...], slowly and cleanly decomposes in cyclohexane to give methylcyclopentane and a yellow crystalline precipitate. The [...] NMR spectrum of the yellow product is consistent with a compound containing one [...] and one [...], the latter arising via metallation of a [...] ligand (i.e. a \"tuck-in\" complex). The structure of the complex which crystallizes as the dimer, [...], when allowed to form slowly at room temperature is reported.\n\nReaction of the neutral ligand 1,4,7-trimethyl-1,4,7-triazacyclononane (Cn) with [...] in acetonitrile affords the novel trihalide complexes [...]. Subsequent alkylation with [...] in THF cleanly gives the corresponding trimethyl species [...]. Reactivity studies reveal that the metal carbon bonds of these 12 [...] complexes are remarkably unreactive toward insertion chemistry with typical unsaturated substrates such as olefins and acetylene. 2-butyne does, however, react with [...] by C-H activation to give a compound that is characterized as an equilibrium mixture of a major allenyl form with a minor propargyl component. In general, [...] is significantly more stable, but less reactive, than [...]. Activation of [...] with [...] or [...] results in partially characterized complexes which exhibit olefin polymerization chemistry. The crystal structure of [...] has been determined.\n\nWe have recently described the highly iso-specific Ziegler-Natta polymerization of [alpha]-olefins using the single component, [...] symmetric metallocene [...]. The steric bias exerted by the cyclopentadienyl substitution pattern allows for formation of only the desired racemic product upon metallation, with no detectable amount of the undesired meso isomer. A natural extension is the further development of methods for obtaining enantiomerically pure catalysts based on the [Bp] ligand system. Such single-component systems, in addition to serving as powerful mechanistic probes of Ziegler-Natta catalysis, would also be promising candidates for use in a variety of other catalytic asymmetric transformations. The most desirable ligand design would produce only one enantiomer upon coordination to the metal. Thus, not only would the wasteful and tedious separation of the meso isomer be avoided, but the subsequent resolution of the racemate would also be obviated. We have found that employment of chiral silyl-linkers is an effective design strategy for the synthesis of such enantiomerically pure complexes. Described herein are our efforts which have led to the synthesis of the ligand [...], designed to coordinate to give only one enantiomer, and BnBpY-H, the first example, as far as we are aware, of an enantiopure [...]-symmetric, group III metallocene which is competent for coordination polymerization of [alpha]-olefins.\n", "date": "1995", "date_type": "degree", "id_number": "CaltechETD:etd-10052007-131102", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechETD:etd-10052007-131102", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "deposited_by": "Imported from ETD-db", "deposited_on": "2007-10-19", "doi": "10.7907/9nxq-m253", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "chair" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_submitted_date": "2007-10-05", "thesis_defense_date": "1995-05-25", "thesis_approved_date": "2007-10-19", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive\nlicense to archive and make accessible, under the conditions specified below,\nmy thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1995", "author_list": "Hajela, Sharad", "advisor_list": "Bercaw, John E.", "comittee_list": "Bercaw, John E." }, { "id": "https://thesis.library.caltech.edu/id/eprint/3473", "eprint_id": 3473, "rev_number": 9, "documents": [ { "id": "/id/document/6016", "doc_id": 6016, "rev_number": 3, "files": [ { "id": "/id/file/35871", "fileid": 35871, "datasetid": "document", "objectid": 6016, "filename": "Birnbaum_er_1995.pdf", "mime_type": "application/pdf", "filesize": 11793411, "mtime": "2012-12-26 03:00:12", "url": "/3473/1/Birnbaum_er_1995.pdf" } ], "eprint_id": 3473, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "format_desc": "Birnbaum_er_1995.pdf", "language": "en", "security": "public", "license": "other", "main": "Birnbaum_er_1995.pdf", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "final", "relation": { "items": [ { "type": "http://eprints.org/relation/hasVolatileVersion", "uri": "/id/document/22556" }, { "type": "http://eprints.org/relation/haspreviewThumbnailVersion", "uri": "/id/document/22556" }, { "type": "http://eprints.org/relation/hasVersion", "uri": "/id/document/22556" } ] } }, { "id": "/id/document/22556", "doc_id": 22556, "rev_number": 3, "files": [ { "id": "/id/file/35869", "fileid": 35869, "datasetid": "document", "objectid": 22556, "filename": "preview.png", "mime_type": "image/png", "hash": "87e4601cd06a4bffa135ff97e49c2573", "hash_type": "MD5", "filesize": 10547, "mtime": "2012-12-26 03:00:12", "url": "/3473/2/preview.png" } ], "eprint_id": 3473, "pos": 2, "placement": 2, "mime_type": "image/png", "format": "image/png", "language": "en", "security": "public", "license": "other", "main": "preview.png", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/6016" }, { "type": "http://eprints.org/relation/ispreviewThumbnailVersionOf", "uri": "/id/document/6016" }, { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/6016" } ] } } ], "eprint_status": "archive", "userid": 2, "dir": "disk0/00/00/34/73", "datestamp": "2007-09-25", "lastmod": "2021-04-16 23:11:42", "status_changed": "2009-09-25 02:58:58", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Birnbaum-E-R", "name": { "family": "Birnbaum", "given": "Eva Rachel" }, "show_email": "NO" } ] }, "title": "The mechanism of catalytic hydrocarbon oxidation by molecular oxygen and halogenated ruthenium and iron porphyrins", "ispublished": "unpub", "full_text_status": "public", "abstract": "NOTE: Text or symbols not renderable in plain ASCII are indicated by [...]. Abstract is included in .pdf document.\n\nHighly halogenated ruthenium and iron porphyrins are shown to be active catalysts for alkene oxidation with dioxygen or iodosobenzene. The synthesis and characterization of [...]-octachloro-tetrakis(pentafluorophenyl)porphyrinato-ruthenium(II) carbonyl [RuTFPPCl[...](CO)] and [...]-octabromo-tetrakis(pentafluorophenyl)porphyrinato-iron(III) chloride [Fe(TIPPBr[...])Cl] are reported. Crystal structures of RuTFPPC1[...](CO) and the zinc and free ligand precursor complexes show extensive distortion of the halogenated porphyrin macrocycles due to steric interactions between the b-chlorine atoms and the pentafluorophenyl rings. [...]FNMR is developed as a method to characterize both paramagnetic and diamagnetic fluorinated porphyrins in solution. The anodically shifted reduction potentials and red shifted absorptions in the UV-Vis spectroscopy of the halogenated porphyrins are discussed in terms of steric and electronic effects on porphyrin frontier orbitals.\n\nBoth Fe(TFPPBr[...])Cl and RuTFPPCl[...](CO) catalyze the oxidation of cyclohexene with dioxygen and without added coreductant, with 73 and 296 turnovers, respectively, in 24 hours. Although both porphyrins will catalyze reactions with iodosobenzene, showing selectivity consistent with high-valent metal-oxo formation, overall activity with dioxygen is much higher. In accord with earlier work, cyclohexene oxidation by Fe(TFPPBr[...])Cl is consistent with a mechanism involving porphyrin-mediated decomposition of alkyl peroxides, which generates free radicals in solution. Catalysis with RuTFPPCl[...](CO) is shown to be of a photochemical nature, as irradiation with low energy light results in a dramatic increase in the reaction rate. A reaction mechanism involving olefin binding to the excited ruthenium porphyrin is suggested by laser photolysis experiments. This catalyst represents the first stable, effective metalloporphyrin catalyst for olefin oxidation with dioxygen and light.\n", "date": "1995", "date_type": "degree", "id_number": "CaltechETD:etd-09112007-142146", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechETD:etd-09112007-142146", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "deposited_by": "Imported from ETD-db", "deposited_on": "2007-09-25", "doi": "10.7907/55r8-tt83", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "name": { "family": "Unknown", "given": "Unknown" } } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_submitted_date": "2007-09-11", "thesis_defense_date": "1995-05-08", "thesis_approved_date": "2007-09-25", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive\nlicense to archive and make accessible, under the conditions specified below,\nmy thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1995", "author_list": "Birnbaum, Eva Rachel", "advisor_list": "Bercaw, John E. and Gray, Harry B.", "comittee_list": "Unknown, Unknown" }, { "id": "https://thesis.library.caltech.edu/id/eprint/7169", "eprint_id": 7169, "rev_number": 21, "documents": [ { "id": "/id/document/15152", "doc_id": 15152, "rev_number": 7, "files": [ { "id": "/id/file/98864", "fileid": 98864, "datasetid": "document", "objectid": 15152, "filename": "Quan_rw_1994.pdf", "mime_type": "application/pdf", "filesize": 21464672, "mtime": "2012-12-26 04:44:36", "url": "/7169/1/Quan_rw_1994.pdf" } ], "eprint_id": 7169, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": "Quan_rw_1994.pdf", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "final", "relation": { "items": [ { "type": "http://eprints.org/relation/hasVolatileVersion", "uri": "/id/document/28137" }, { "type": "http://eprints.org/relation/haspreviewThumbnailVersion", "uri": "/id/document/28137" }, { "type": "http://eprints.org/relation/hasVersion", "uri": "/id/document/28137" } ] } }, { "id": "/id/document/15153", "doc_id": 15153, "rev_number": 3, "files": [ { "id": "/id/file/207986", "fileid": 207986, "datasetid": "document", "objectid": 15153, "filename": "Quan_rw_1994.zip", "mime_type": "application/zip", "filesize": 71776817, "mtime": "2016-08-22 21:24:12", "url": "/7169/2/Quan_rw_1994.zip" } ], "eprint_id": 7169, "pos": 2, "format": "application/zip", "language": "en", "security": "internal", "license": "other", "main": "Quan_rw_1994.zip", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "final" }, { "id": "/id/document/28137", "doc_id": 28137, "rev_number": 3, "files": [ { "id": "/id/file/98862", "fileid": 98862, "datasetid": "document", "objectid": 28137, "filename": "preview.png", "mime_type": "image/png", "hash": "2bfad10427aa55eff3b8058572ef8005", "hash_type": "MD5", "filesize": 27777, "mtime": "2012-12-26 04:44:36", "url": "/7169/3/preview.png" } ], "eprint_id": 7169, "pos": 3, "placement": 3, "mime_type": "image/png", "format": "image/png", "language": "en", "security": "public", "license": "other", "main": "preview.png", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/15152" }, { "type": "http://eprints.org/relation/ispreviewThumbnailVersionOf", "uri": "/id/document/15152" }, { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/15152" } ] } }, { "id": "/id/document/127615", "doc_id": 127615, "rev_number": 1, "files": [ { "id": "/id/file/373051", "fileid": 373051, "datasetid": "document", "objectid": 127615, "filename": "indexcodes.txt", "mime_type": "text/plain", "hash": "106110af4643b2912e15937beac67135", "hash_type": "MD5", "filesize": 29035, "mtime": "2021-06-24 01:54:39", "url": "/7169/4/indexcodes.txt" } ], "eprint_id": 7169, "pos": 4, "placement": 4, "mime_type": "text/plain", "format": "other", "format_desc": "Generate index codes conversion from application/pdf to indexcodes", "language": "en", "security": "public", "license": "other", "main": "indexcodes.txt", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/15152" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/15152" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/15152" } ] } } ], "eprint_status": "archive", "userid": 50, "dir": "disk0/00/00/71/69", "datestamp": "2012-07-05 23:26:01", "lastmod": "2021-04-16 23:00:05", "status_changed": "2012-07-05 23:26:01", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Quan-R-W", "name": { "family": "Quan", "given": "Roger Weihong" }, "show_email": "NO" } ] }, "title": "Oxo, imido, and borollide complexes of tantalum and zirconium", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "The preparation of reactive oxo, imido, and borollide complexes on tantalum and zirconium will be described. Metathesis of Cp*2Ta(=O)Cl with AgPF6 afforded [Cp*2TaF2HPF6], which presumably formed from P-F activation of PF6-. When AgS03CF3 was used, [Cp*2Ta(=O)][S03CF3] was isolated; however, it was unreactive toward styrene, methane, or benzene. Exposure to water resulted in the 1,2-addition product, [Cp*2Ta(OH)2][S03CF3]. Finally, treating Cp*2Ta(=O)H with [Ph3C][B(C6F5)4] afforded [Cp*2Ta(=O)][B(C6F5)4]. Even with this non-coordinating counterion, the complex was found to be surprisingly unreactive. To prepare an imido complex, treating Cp*TaCl4 with four equivalents of lithium anilide affords Cp*Ta(=NPh)(NHPh)2. This complex reacts readily with substituted anilines to generate Cp*Ta(=NPh')(NHPh')2 and with alcohols such as pinacol to afford Cp*Ta(OCMe2CMe2O)2, products whereby both the imido and amido groups are exchanged. Exposing Cp*Ta(=NPh)(NHPh)2 to C02 resulted in the isolation of Cp*Ta(OCONPh)(\u03b74-OCONHPh)2 with both the formal [2+2] addition of C02 across the imido group and insertion of C02 into the amido group. Finally, bis-imido complexes were prepared by treating Cp*Ta(=NPh)(NHPh)2 to one equivalent of HCl to yield Cp*Ta(=NPh)2 or by treating Cp*TaCl4 with four equivalents of lithium 2,6-diisopropylanilide to yield Cp*Ta(=NPh\")2. The borollide ligand, (C4H4BNiPr2)2-, ligand is introduced by treating Cp*ZrCl3 with one equivalent of Li2(C4H4BNiPr2)\u2022THF to generate Cp*(C4H4BNiPr2)ZrCl\u2022LiCl. This complex contains a \u03b75- coordinated borollide ligand, as shown by an X-ray crystal structure analysis. Alkylation and arylation with trimethylsilylmethyllithium, benzylpotassium or phenyllithium yielded Cp*(C4H4BNiPr2)ZrR complexes. These catalysts polymerizes ethylene, but only oligomerizes \u03b1-olefins. In addition, Cp*(C4H4BNiPr2)ZrCl\u2022LiCl has been found to exhibit the formal heterolytic cleavage of HCl and CH3I, affording Cp*(C4H4BNHiPr2)ZrCl2 and Cp*(C4H4BNiPr2)ZrCl(I), respectively. Finally, treatment of Cp*(C4H4BNiPr2)ZrCl\u2022LiCl with LiNHtBu generated the zwitterionic complex, Cp*(C4H4BNHiPr2)Zr=NtBu.\r\n\r\n", "date": "1994", "date_type": "degree", "id_number": "CaltechTHESIS:07052012-161238837", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:07052012-161238837", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "BP", "deposited_on": "2012-07-05 23:26:01", "doi": "10.7907/0351-pe35", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "name": { "family": "Unknown", "given": "Unknown" } } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1993-11-01", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1994", "author_list": "Quan, Roger Weihong", "advisor_list": "Bercaw, John E.", "comittee_list": "Unknown, Unknown" }, { "id": "https://thesis.library.caltech.edu/id/eprint/7660", "eprint_id": 7660, "rev_number": 20, "documents": [ { "id": "/id/document/37900", "doc_id": 37900, "rev_number": 3, "files": [ { "id": "/id/file/117616", "fileid": 117616, "datasetid": "document", "objectid": 37900, "filename": "Kelson 1994.pdf", "mime_type": "application/pdf", "hash": "f4326856f549015c77785d1758686c53", "hash_type": "MD5", "filesize": 26549243, "mtime": "2013-05-03 17:54:20", "url": "/7660/1/Kelson 1994.pdf" } ], "eprint_id": 7660, "pos": 1, "placement": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": "Kelson 1994.pdf", 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"/id/document/128156", "doc_id": 128156, "rev_number": 1, "files": [ { "id": "/id/file/373592", "fileid": 373592, "datasetid": "document", "objectid": 128156, "filename": "indexcodes.txt", "mime_type": "text/plain", "hash": "ca0f1e8a7874b6b57f9c2bce78479a28", "hash_type": "MD5", "filesize": 33610, "mtime": "2021-06-24 02:34:28", "url": "/7660/7/indexcodes.txt" } ], "eprint_id": 7660, "pos": 7, "placement": 7, "mime_type": "text/plain", "format": "other", "format_desc": "Generate index codes conversion from application/pdf to indexcodes", "language": "en", "security": "public", "license": "other", "main": "indexcodes.txt", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/37900" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/37900" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/37900" } ] } } ], "eprint_status": "archive", "userid": 50, "dir": "disk0/00/00/76/60", "datestamp": "2013-05-03 18:07:07", "lastmod": "2022-11-09 19:20:00", "status_changed": "2013-05-03 18:07:07", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Kelson-E-P", "name": { "family": "Kelson", "given": "Eric P." }, "show_email": "NO" } ] }, "title": "The electrocatalytic and stoichiometric oxidation chemistry of binuclear ruthenium complexes incorporating the anionic tripod ligand {(\u03b75-C5H5)Co[P(OCH3)2(=O)]3}-\r ", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "The anionic tripod ligand NaLoMe (L_(oMe) - = [(\u03b7^5-C_5H_5)Co{P(O)(OCH_3)_2}_3]^-) reacts\r\nwith RuO_4 in a biphasic reaction mixture of 1% H_2SO_4 and CCI_4 to afford [(L_(oMe) (HO)Ru^(IV)\r\n(\u00b5-O)_2Ru ^(IV)(OH)(L_(oMe)] (1), which is treated with aqueous CF_3S0_3H to generate\r\n[(L_(oMe)(H_2O)Ru^(IV) (\u00b5-O)_2R^(IV) (OH_2)(L_(oMe)][CF_3SO_3]_2 ([H_21][CF_3SO_3]_2). \r\nAddition of iodosobenzene to an acetonitrile solution of this salt yields [(L_(oMe)(O)Ru^v(\u00b5-0)2Ru^v-(O)(_(LoMe)] (2). The dimer 1 can be reduced chemically or electrochemically to the Ru^(III)- Ru^(III)\r\ndimers [(L_(oMe)(H_20)Ru^(III) (\u00b5-OH)_2Ru^(III) (OH_2)(L_(oMe)) ]^2+ and [(L_(oMe)) ^(III) (\u00b5-0Hh(\u00b5-0H2)Ru^(III) (L_(oMe)]^2+ which interconvert in aqueous media. Two electron processes dominate both the bulk chemistry and the electrochemistry of 1. Among these processes are the quasi-reversible\r\nRu^(IV) - Ru^(IV)/Ru^(III)- Ru^(III) and Ru^(III)- Ru^(III)/ Ru^(II)- Ru^(II) reductions and a largely irreversible\r\nRu^(V) - Ru^(V)/ Ru^(IV) - Ru^(IV)/oxidation. The dioxo dimer 2 oxidizes alcohols and aldehydes in organic\r\nmedia to afford 1 and the corresponding aldehydes and acids. Analogously, the Ru^(V) - Ru^(V)/ Ru^(IV)- Ru^(IV)\r\nredox wave mediates the electrooxidation of alcohols and aldehydes in aqueous buffer. In\r\nthis system, substrates can be oxidized completely to CO_2. The kinetic behavior of these\r\noxidations was examined by UV-vis and chronoamperometry, respectively, and the chemistry\r\nis typical of metal-oxo complexes, indicating that electronic coupling between two metal centers\r\ndoes not dramatically affect the metal-oxo chemistry. Dimer [H_21]^(2+) also reacts with\r\nalcohols, aldehydes, and triphenylphosphine in CH_3CN to afford Ru^(III)- Ru^(III) products\r\nincluding [(L_(oMe))CH_3CN) Ru^(III) (\u00b5-OH)_2 Ru^(III) (NCCH_3)( L_(oMe))][CF_3SO_3]2 (characterized by X-ray\r\ncrystallography) and the corresponding organic products. Reaction of 1 with formaldehyde\r\nin aqueous buffer quantitatively affords the triply bridged dimer [(L_(oMe)Ru^(III) (\u00b5-OH)2-\r\n(\u00b5-HCOO) Ru^(III) (L_(oMe)][CF_3SO_3] (characterized by X-ray crystallography). This reaction\r\nevidently proceeds by two parallel inner-sphere pathways, one of which is autocatalytic.\r\nNeither pathway exhibits a primary isotope effect suggesting the rate determining process\r\ncould be the formation of an intermediate, perhaps a Ru^(IV) - Ru^(IV) formate adduct. The Ru^(III)- Ru^(III)formate adduct is easily oxidized to the Ru^(IV) - Ru^(IV) analog \r\n[(L_(oMe)Ru^(IV)(\u00b5-OH)_2-(\u00b5-HCOO) Ru^(IV) (L_(oMe)][CF_3SO_3], which, after isolation, reacts slowly with aqueous formaldehyde to\r\ngenerate free formate and the Ru^(III)- Ru^(III) formate adduct. These dimers function as catalysts for\r\nthe electrooxidation of formaldehyde at low anodic potentials (+0.0 V versus SCE in aqueous\r\nbuffer, pH 8.5) and enhance the activity of Nafion treated palladium/carbon heterogeneous\r\nfuel cell catalysts.\r\n\r\n", "date": "1994", "date_type": "degree", "id_number": "CaltechTHESIS:05032013-095024526", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:05032013-095024526", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Tony Diaz", "deposited_on": "2013-05-03 18:07:07", "doi": "10.7907/xmwk-dk48", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "name": { "family": "Unknown", "given": "Unknown" } } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1993-09-03", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1994", "author_list": "Kelson, Eric P.", "advisor_list": "Bercaw, John E.", "comittee_list": "Unknown, Unknown" }, { "id": "https://thesis.library.caltech.edu/id/eprint/7648", "eprint_id": 7648, "rev_number": 15, "documents": [ { "id": "/id/document/37601", "doc_id": 37601, "rev_number": 3, "files": [ { "id": "/id/file/117157", "fileid": 117157, "datasetid": "document", "objectid": 37601, "filename": "Coughlin_eb_1994.zip", "mime_type": "application/x-zip", "hash": "ecdf604146516d8483ec05299b98155f", "hash_type": "MD5", "filesize": 117388601, "mtime": "2013-05-01 18:35:48", "url": "/7648/1/Coughlin_eb_1994.zip" } ], "eprint_id": 7648, "pos": 1, "placement": 1, "mime_type": "application/x-zip", "format": "application/zip", "format_desc": "TIFF", "language": "en", "security": "internal", "license": "other", 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"/id/document/37602" } ] } }, { "id": "/id/document/128143", "doc_id": 128143, "rev_number": 1, "files": [ { "id": "/id/file/373579", "fileid": 373579, "datasetid": "document", "objectid": 128143, "filename": "indexcodes.txt", "mime_type": "text/plain", "hash": "76260d5d72b316f353d0d11eed481ea4", "hash_type": "MD5", "filesize": 25170, "mtime": "2021-06-24 02:33:24", "url": "/7648/7/indexcodes.txt" } ], "eprint_id": 7648, "pos": 7, "placement": 7, "mime_type": "text/plain", "format": "other", "format_desc": "Generate index codes conversion from application/pdf to indexcodes", "language": "en", "security": "public", "license": "other", "main": "indexcodes.txt", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/37602" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/37602" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/37602" } ] } } ], "eprint_status": "archive", "userid": 87, "dir": "disk0/00/00/76/48", "datestamp": "2013-05-01 19:29:08", "lastmod": "2022-11-09 19:19:59", "status_changed": "2013-05-01 19:29:08", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Coughlin-E-B", "name": { "family": "Coughlin", "given": "E. Bryan" }, "show_email": "NO" } ] }, "title": "Iso-specific Ziegler-Natta polymerization of \u03b1-olefins with a single-component organoyttrium catalyst", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "The synthesis of a sterically tailored ligand array\r\n(M)_2((C_5H_2-2-Si(CH_3)_3-4-C(CH_3)_3)S_2i(CH_3)_2](\"M_2Bp\") (M = Li, 16; K, 19) is\r\ndescribed. Transmetallation of Li_2Bp with YCl_3(THF)_3 affords exclusively the\r\nC_2 symmetric product rac-[BpY(\u00b5_2-Cl)_2Li(THF)_2], 20. A X-ray crystal structure\r\nof 20 has been determined; triclinic, P1, a= 13.110 (8), b = 17.163 (15), c = 20.623\r\n(14) \u00c5, \u03b1 = 104.02 (7), \u03b2 = 99.38 (5), \u03b3 = 100.24 (6)\u00b0 , Z = 4, R = 0.056.\r\nTransmetallation of K_2Bp with YCl_3(THF)_3 affords the halide free complex\r\nrac-BpYCl, 23. The corresponding rac-BpLaCl, 28, is prepared in an anlogous\r\nmanner. In all cases the achiral meso isomer is not obtained since only for\r\nthe racemic isomers are the unfavorable steric interactions between the\r\nSi(CH3)_3 groups in the narrow portion of the [Cp-M'-Cp] wedge avoided.\r\nAlkylation of 20 or 23 with LiCH(Si(CH_3)_3)_2 affords rac-BpYCH(Si(CH_3)_3)_2, 26\r\nin good yield. Alkylation of 28 with LiCH(Si(CH_3)_3)_2 affords\r\nrac-BpLaCH(Si(CH_3)_3)_2 29. Hydrogenation of 26 cleanly affords the bridging\r\nhydride species [BpY(\u00b5_2-H)]_2, 27, as the homochiral (R,R) and (S,S) dimeric\r\npairs. 26 is an efficient initiator for the polymerization of ethylene to high\r\nmolecular weight linear polyethylene. 27 catalyzes the polymerization of\r\npropylene (25% v/v in methylcyclohexane) and neat samples of 1-butene,\r\n1-pentene, 1-hexene to moderately high molecular weight polymers:\r\npolypropylene (M_n = 4,200, PDI 2.32, T_m 157 \u00b0C); poly-1-butene (M_n = 8,500, PDI\r\n3.44, T_m 105 \u00b0C); poly-1-pentene (M_n = 20,000, PDI 1.99, T_m 73 \u00b0C);\r\npoly-1-hexene (M_n = 24,000, PDI 1.75, T_m < 25 \u00b0C). ^(13)C NMR spectra at the\r\npentad analysis level indicates that the degree of isotacticity is 99% mmmm\r\nfor all polymer samples. 27 is the first single component iso-specific \u03b1-olefin\r\npolymerization catalyst. The presumed origins of the high isospecificity are\r\npresented.", "date": "1994", "date_type": "degree", "id_number": "CaltechTHESIS:05012013-111738760", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:05012013-111738760", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Tony Diaz", "deposited_by": "Benjamin Perez", "deposited_on": "2013-05-01 19:29:08", "doi": "10.7907/djm5-zt75", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "name": { "family": "Unknown", "given": "Unknown" } } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1993-07-16", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1994", "author_list": "Coughlin, E. Bryan", "advisor_list": "Bercaw, John E.", "comittee_list": "Unknown, Unknown" }, { "id": "https://thesis.library.caltech.edu/id/eprint/7291", "eprint_id": 7291, "rev_number": 17, "documents": [ { "id": "/id/document/16509", "doc_id": 16509, "rev_number": 3, "files": [ { "id": "/id/file/208064", "fileid": 208064, "datasetid": "document", "objectid": 16509, "filename": "Cotter_wd_1993.zip", "mime_type": "application/zip", "filesize": 70360334, "mtime": "2016-08-22 21:24:24", "url": "/7291/1/Cotter_wd_1993.zip" } ], "eprint_id": 7291, "pos": 1, "format": "application/zip", "format_desc": "TIFF", "language": "en", "security": "internal", "license": "other", "main": "Cotter_wd_1993.zip", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "final" }, { "id": "/id/document/16510", "doc_id": 16510, "rev_number": 5, "files": [ { "id": "/id/file/101506", "fileid": 101506, "datasetid": "document", "objectid": 16510, "filename": "Cotter_wd_1993.pdf", "mime_type": "application/pdf", "filesize": 37695031, "mtime": "2012-12-26 04:46:05", "url": "/7291/2/Cotter_wd_1993.pdf" } ], "eprint_id": 7291, "pos": 2, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": "Cotter_wd_1993.pdf", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "final", "relation": { "items": [ { "type": "http://eprints.org/relation/hasVolatileVersion", "uri": "/id/document/28250" }, { "type": "http://eprints.org/relation/haspreviewThumbnailVersion", "uri": "/id/document/28250" }, { "type": "http://eprints.org/relation/hasVersion", "uri": "/id/document/28250" } ] } }, { "id": "/id/document/28250", "doc_id": 28250, "rev_number": 3, "files": [ { "id": "/id/file/101504", "fileid": 101504, "datasetid": "document", "objectid": 28250, "filename": "preview.png", "mime_type": "image/png", "hash": "b076e64f34f051fac0cdda7118e4861a", "hash_type": "MD5", "filesize": 39572, "mtime": "2012-12-26 04:46:05", "url": "/7291/3/preview.png" } ], "eprint_id": 7291, "pos": 3, "placement": 3, "mime_type": "image/png", "format": "image/png", "language": "en", "security": "public", "license": "other", "main": "preview.png", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/16510" }, { "type": "http://eprints.org/relation/ispreviewThumbnailVersionOf", "uri": "/id/document/16510" }, { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/16510" } ] } }, { "id": "/id/document/127748", "doc_id": 127748, "rev_number": 1, "files": [ { "id": "/id/file/373184", "fileid": 373184, "datasetid": "document", "objectid": 127748, "filename": "indexcodes.txt", "mime_type": "text/plain", "hash": "9835f9564a403a3dd95160b29d5ee209", "hash_type": "MD5", "filesize": 38379, "mtime": "2021-06-24 02:02:29", "url": "/7291/4/indexcodes.txt" } ], "eprint_id": 7291, "pos": 4, "placement": 4, "mime_type": "text/plain", "format": "other", "format_desc": "Generate index codes conversion from application/pdf to indexcodes", "language": "en", "security": "public", "license": "other", "main": "indexcodes.txt", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/16510" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/16510" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/16510" } ] } } ], "eprint_status": "archive", "userid": 87, "dir": "disk0/00/00/72/91", "datestamp": "2012-11-28 22:32:14", "lastmod": "2022-11-09 19:20:01", "status_changed": "2012-11-28 22:32:14", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Cotter-W-D", "name": { "family": "Cotter", "given": "W. Donald" }, "show_email": "NO" } ] }, "title": "Organoscandium complexes as mechanistic probes in the Ziegler-Natta polymerization of \u03b1-olefins and dienes", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry ", "abstract": "Measurement of the molecular-weight distributions of alkanes prepared by treatment\r\nof permethylscandocene alkyl complexes at -78\u00b0C reveals that under the reaction conditions the\r\nreaction may be described as \"living.\"
\r\n\r\nThe stoichiometric insertion of 2-butyne across the scandium-carbon \u03c3-bond in Cp*_2ScCH_3\r\nproceeds without a visible kinetic deuterium isotope effect, either for substitution at the alkyne\r\nmethyl groups or at the scandium-methyl group. The first result reveals that steric isotope\r\neffects are not important in this reaction, which models the propagation step in Ziegler-Natta\r\npolymerization. The second result suggests that an \u03b1-agostic interaction is likely not present in\r\nthe transition state for 2-butyne insertion.
\r\n\r\nThe polymerization of conjugated dienes with organoscandium complexes of the type {[(\u03b7^5-\r\nC_5Me_4)SiMe_2NCMe_3]ScR}_2 (R = n-propyl, n-butyl) leads to polymers with very narrow\r\nmolecular-weight distributions and microstructures rich in 1,2-repeat units and an unusual\r\ncyclic repeat unit derived from two sequential 1,2-insertions. The 1,4-repeat unit characteristic\r\nof rubber account for about 40 mass-% of the products. Allyl complexes are readily prepared\r\nfrom treatment of alkylscandium complexes with conjugated dienes, or from treatment of the\r\nscandium hydride complex {[(\u03b7^5-C_5Me_4)SiMe_2NCMe_3]ScH(PMe_3)}_2 with allenes. This hydride\r\ncomplex, however, reacts with butadiene to form an ethylene-bridged complex and ethane.
\r\n\r\nBoth the hydride complex {[(\u03b7^5-C_5Me_4)SiMe_2NCMe_3]ScR}_2 and the alkyl complex {[(\u03b7^5-\r\nC_5Me_4)SiMe_2NCMe_3]Sc(CH_2CH_2CH_3)]_2 catalyze the cyclopolymerization of 1,5-hexadiene.\r\nAlthough polymers with narrow molecular weight distributions (1.1-1.2) can be obtained, the\r\npolydispersity index is very sensitive to the presence of trimethylphosphine and, to a lesser\r\nextent, to the nature of the initiating group. Chain-transfer processes could not be studied\r\ndirectly due to deleterious reactivity with scandium-hydride trapping reagents.\r\nCyclopolymerization is not accompanied by a measurable a deuterium isotope effect on the\r\ncyclization step, which suggests that trans-fused [5,4]-bicyclic transition states are allowed for\r\nthis step.
\r\n\r\nVariable-temperature NMR spectroscopy was used to examine the dynamic solution behavior\r\nof several ansa-(cyclopentadienyl)amidoscandium alkyl complexes. On the basis of these\r\nstudies, it is proposed that the primary equilibrium when trimethylphosphine is present is\r\nbetween a phosphine-bound scandium alkyl and a free, 12-electron monomeric scandium alkyl.
", "date": "1993", "date_type": "degree", "id_number": "CaltechTHESIS:11282012-135537271", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:11282012-135537271", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Tony Diaz", "deposited_by": "Benjamin Perez", "deposited_on": "2012-11-28 22:32:14", "doi": "10.7907/9wx4-9x03", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "name": { "family": "Unknown", "given": "Unknown" } } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1992-12-11", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1993", "author_list": "Cotter, W. Donald", "advisor_list": "Bercaw, John E.", "comittee_list": "Unknown, Unknown" }, { "id": "https://thesis.library.caltech.edu/id/eprint/6699", "eprint_id": 6699, "rev_number": 12, "documents": [ { "id": "/id/document/13675", "doc_id": 13675, "rev_number": 4, "files": [ { "id": "/id/file/88786", "fileid": 88786, "datasetid": "document", "objectid": 13675, "filename": "Haney_se_1992.pdf", "mime_type": "application/pdf", "filesize": 4304888, "mtime": "2012-12-26 04:38:57", "url": "/6699/1/Haney_se_1992.pdf" } ], "eprint_id": 6699, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": "Haney_se_1992.pdf", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "final" }, { "id": "/id/document/13676", "doc_id": 13676, "rev_number": 3, "files": [ { "id": "/id/file/207546", "fileid": 207546, "datasetid": "document", "objectid": 13676, "filename": "Haney_se_1992.zip", "mime_type": "application/zip", "filesize": 10891908, "mtime": "2016-08-22 21:23:16", "url": "/6699/2/Haney_se_1992.zip" } ], "eprint_id": 6699, "pos": 2, "format": "application/zip", "format_desc": "TIFF", "language": "en", "security": "internal", "license": "other", "main": "Haney_se_1992.zip", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "final" }, { "id": "/id/document/127069", "doc_id": 127069, "rev_number": 1, "files": [ { "id": "/id/file/372503", "fileid": 372503, "datasetid": "document", "objectid": 127069, "filename": "indexcodes.txt", "mime_type": "text/plain", "hash": "8da14df64c9fffd49efe2e1849ca670a", "hash_type": "MD5", "filesize": 9787, "mtime": "2021-06-24 01:24:23", "url": "/6699/3/indexcodes.txt" } ], "eprint_id": 6699, "pos": 3, "placement": 3, "mime_type": "text/plain", "format": "other", "format_desc": "Generate index codes conversion from application/pdf to indexcodes", "language": "en", "security": "public", "license": "other", "main": "indexcodes.txt", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/13675" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/13675" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/13675" } ] } } ], "eprint_status": "archive", "userid": 51, "dir": "disk0/00/00/66/99", "datestamp": "2011-10-03 21:21:45", "lastmod": "2021-04-16 23:02:42", "status_changed": "2011-10-03 21:21:45", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Haney-S-E", "name": { "family": "Haney", "given": "Susan Elaine" }, "show_email": "NO" } ] }, "title": "Investigation of low-valent ruthenium aquo complexes", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "The work presented in this thesis investigates the synthesis of low oxidation state coordination complexes of ruthenium incorporating the anionic ligand, [CpCo(P(O)(OMe)_2)_3]-,(L_(OMe)). Several routes to RuL_(OMe)(H_2O)_3^+ are outlined. These routes produced two major products, possibly related by acid-base chemistry.
\r\n\r\nA new dimeric ruthenium aquo species with the proposed structure [Ru(III)L_(OMe)(H_2O)(\u00b5-OH)_2OTs_2 was isolated. This complex does not provide a straightforward route to the target monomeric oxo compounds, but could conceivably provide a entry into synthesis of ruthenium dimers containing arnines and other ligands.
\r\n\r\nFinally, a new route to [Ru(IV)(H_20)(\u00b5-O)]_2OTf_2 was discovered which is more convenient and is higher yielding than the previously published procedure.
", "date": "1992", "date_type": "degree", "id_number": "CaltechTHESIS:10032011-090148072", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:10032011-090148072", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "deposited_by": "Tony Diaz", "deposited_on": "2011-10-03 21:21:45", "doi": "10.7907/bd27-j183", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "masters", "thesis_advisor": { "items": [ { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "name": { "family": "Unknown", "given": "Unknown" } } ] }, "thesis_degree": "MS", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1992-01-01", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1992", "author_list": "Haney, Susan Elaine", "advisor_list": "Bercaw, John E.", "comittee_list": "Unknown, Unknown" }, { "id": "https://thesis.library.caltech.edu/id/eprint/11892", "eprint_id": 11892, "rev_number": 20, "documents": [ { "id": "/id/document/104149", "doc_id": 104149, "rev_number": 3, "files": [ { "id": "/id/file/310905", "fileid": 310905, "datasetid": "document", "objectid": 104149, "filename": "shapiro_pj_1991.pdf", "mime_type": "application/pdf", "hash": "0a8cdfb9d54e3d349c0f37d5fcee4afe", "hash_type": "MD5", "filesize": 5234808, "mtime": "2019-11-05 17:28:12", "url": "/11892/1/shapiro_pj_1991.pdf" } ], "eprint_id": 11892, "pos": 1, "placement": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": 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"0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/104149" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/104149" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/104149" } ] } } ], "eprint_status": "archive", "userid": 8820, "dir": "disk0/00/01/18/92", "datestamp": "2019-11-05 17:47:19", "lastmod": "2021-04-16 23:06:49", "status_changed": "2019-11-05 17:47:19", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Shapiro-Pamela-Joy", "name": { "family": "Shapiro", "given": "Pamela Joy" }, "show_email": "NO" } ] }, "title": "Part I. Scandium Hydride and Alkyl Complexes with a Linked Monocyclopentadienyl-Amido Ligand-Framework: Single Component Catalysts for the Polymerization of \u03b1-Olefins. Part II. Hydrazido(1-) and 2,2-Dimethylhydrazido(1-) Derivatives of Permethylscandocene. Preparation and Structural Characterization of their Products from Reactions with Acetonitrile", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "Various monocyclopentadienyl scandium amido derivatives with the general formulas {(\u03b75-C5Me4)SiMe2(\u03b71-NCMe3}ScR, (Cp*SiNR)ScR, and {(\u03b75-C5H3CMe3)SiMe2(\u03b71-NCMe3}ScR, (tBuCpSiNR)ScR, have been prepared. [(Cp*SiNR)(PMe3)ScH]2 is prepared from the hydrogenation of (Cp*SiNR)ScCH(SiMe3)2 in the presence of PMe3. The scandium hydride effects the multiple insertion of \u03b1-olefins in a controlled fashion to form low molecular weight polymers. \u03b2-H elimination appears to be a principal chain-transfer pathway in this catalyst system. The stoichiometric reaction between [(Cp*SINR)(PMe3)ScH]2 and two equivalents of ethylene produces the ethylene bridged dimer [(Cp*SiNR)(PMe3)Sc]2(\u00b5, \u03b72, \u03b72-C2H4) and an equivalent of ethane. The stoichiometric reaction between the scandium hydride and either propene or butene affords the PMe3-free, alkyl-bridged scandium dimers [(Cp*SiNR)Sc]2(\u00b5-CH2CH2CH3)2 and [(Cp*SiNR)Sc]2(\u00b5-CH2CH2CH2CH3)2. The absence of coordinating phosphine makes these complexes more active olefin polymerization catalysts. The complexes (Cp*SiNR)(PMe3)ScCH2CH(CH)3CH2CH3 and (Cp*SiNR)(PMe3)ScCH(C6H5)CH2CH2CH2(C6H5) have also been prepared and spectroscopically characterized.
\r\n\r\nKinetic analysis of the rate dependence of 1-pentene polymerization by [(Cp*SiNR)(PMe3)ScH]2 on added PMe3 reveals a phosphine dissociation pre-equilibrium to form a PMe3-free active intermediate. The monomeric nature of this intermediate is revealed by the kinetic analysis of 1-pentene polymerization by [(Cp*SiNR)Sc]2(\u00b5-CH2CH2CH3)2 as a function of scandium concentration.
\r\n\r\n(Cp*SiNR)ScR was found to be >99% head-to-tail regioselectfve in the polymerization of propene. Preliminary 13C NMR data indicate lower regioselectivity in propene polymerization by (tBuCpSiNR)ScR. A slight syndiotactic preference is observed in the stereochemistry of the polypropene produced with [(Cp*SiNR)Sc]2(\u00b5-CH2CH2CH3)2. By contrast, [(tBuCpSiNR)ScMe]x displays no stereocontrol, producing an atactic polymer.
\r\n\r\nA rare example of an unsubstituted hydrazido(1-) complex, Cp*2ScNHNH2 (Cp* = (\u03b75-C5Me5)), prepared by reaction of one equivalent of anhydrous hydrazine with Cp*2ScCH3, reacts with acetonitrile to form [chemical formula; see abstract in scanned thesis for details]. The crystal structure of [chemical formula; see abstract in scanned thesis for details] reveals a five-membered, nearly planar [chemical formula; see abstract in scanned thesis for details] ring. The results of a labeling study using 15N=CCH3 are consistent with a mechanism involving insertion of acetonitrile into the Sc-N bond of Cp*2ScNHNH2, followed by tautomerization to form [chemical formula; see abstract in scanned thesis for details]. The closely related compounds Cp*2ScNHNMe2 and [chemical formula; see abstract in scanned thesis for details] have also been prepared, and the structure of the latter compound has been determined.
", "date": "1991", "date_type": "degree", "id_number": "CaltechTHESIS:11042019-173308161", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:11042019-173308161", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Melissa Ray", "other_numbering_system": { "items": [ { "id": "9113620", "name": "UMI" } ] }, "suggestions": "Downloaded from UMI", "deposited_by": "Mel Ray", "deposited_on": "2019-11-05 17:47:19", "doi": "10.7907/hmc3-gy25", "alt_title": { "items": [ "Scandium Hydride and Alkyl Complexes with a Linked Monocyclopentadienyl-Amido Ligand-Framework", "Single Component Catalysts for the Polymerization of \u03b1-Olefins", "Hydrazido(1-) and 2,2-Dimethylhydrazido(1-) Derivatives of Permethylscandocene. Preparation and Structural Characterization of their Products from Reactions with Acetonitrile" ] }, "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "chair" }, { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" }, { "id": "Roberts-J-D", "name": { "family": "Roberts", "given": "John D." }, "role": "member" }, { "email": "rhg@caltech.edu", "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1990-06-19", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1991", "author_list": "Shapiro, Pamela Joy", "advisor_list": "Bercaw, John E.", "comittee_list": "Gray, Harry B.; Bercaw, John E.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/2930", "eprint_id": 2930, "rev_number": 11, "documents": [ { "id": "/id/document/5297", "doc_id": 5297, "rev_number": 4, "files": [ { "id": "/id/file/31080", "fileid": 31080, "datasetid": "document", "objectid": 5297, "filename": "Nelson_je_1991.pdf", "mime_type": "application/pdf", "filesize": 4049173, "mtime": "2012-12-26 02:55:34", "url": "/2930/1/Nelson_je_1991.pdf" } ], "eprint_id": 2930, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": "Nelson_je_1991.pdf", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "final", "relation": { "items": [ { "type": "http://eprints.org/relation/hasVolatileVersion", "uri": "/id/document/21845" }, { "type": "http://eprints.org/relation/haspreviewThumbnailVersion", "uri": "/id/document/21845" }, { "type": "http://eprints.org/relation/hasVersion", "uri": "/id/document/21845" } ] } }, { "id": "/id/document/21845", "doc_id": 21845, "rev_number": 3, "files": [ { "id": "/id/file/31078", "fileid": 31078, "datasetid": "document", "objectid": 21845, "filename": "preview.png", "mime_type": "image/png", "hash": "c17599dd22fc220d9eac54cbd0069e1e", "hash_type": "MD5", "filesize": 10351, "mtime": "2012-12-26 02:55:34", "url": "/2930/2/preview.png" } ], "eprint_id": 2930, "pos": 2, "placement": 2, "mime_type": "image/png", "format": "image/png", "language": "en", "security": "public", "license": "other", "main": "preview.png", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/5297" }, { "type": "http://eprints.org/relation/ispreviewThumbnailVersionOf", "uri": "/id/document/5297" }, { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/5297" } ] } } ], "eprint_status": "archive", "userid": 2, "dir": "disk0/00/00/29/30", "datestamp": "2007-08-02", "lastmod": "2023-01-18 20:09:26", "status_changed": "2009-09-25 02:47:29", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Nelson-Janet-Elizabeth", "name": { "family": "Nelson", "given": "Janet Elizabeth" }, "show_email": "NO" } ] }, "title": "Synthetic, Structural, and Mechanistic Studies in Early Transition Metal and Actinide Chemistry", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "NOTE: Text or symbols not renderable in plain ASCII are indicated by [...]. Abstract is included in .pdf document.\r\n\r\nA series of permethyltantalocene thioaldehyde hydride complexes is prepared by treatment of Cp*2Ta([eta superscript 2]-C6H4)H with thiols. The X-ray structure of Cp*2Ta([eta superscript 2]-S=CHCH2Ph)H is reported. These permethyltantalocene thioaldehyde hydride complexes are shown to be in rapid equilibrium with a 16 electron thiolate species through a beta-H elimination/migration process. Upon heating, the permethyltantalocene thioaldehyde hydride complexes undergo an a-alkyl migration to the thermodynamically favored tautomer, the permethyltantalocene sulfido alkyl, Cp*2Ta(=S)CH2R. Derivatives of the permethyltantalocene phenethylthioaldehyde hydride have been prepared from the erythro- and threo-phenethyl-d2 mercaptan to elucidate the mechanism of this migration. The migration has been found to proceed primarily with retention of stereochemistry at carbon for the migrating alkyl.\r\n\r\nIn contrast to the extremely specific regioselectivity and stereoselectivity normally demonstrated by Schwartz's reagent (Cp2ZrHCl), hydrozirconation of styrene shows two unusual behaviors. First, treatment of Cp2ZrHCl with styrene leads to a mixture of terminal (85%) and internal (15%) insertion products. The benzylic insertion product is stable, and does not undergo migration to a terminal organozirconium product, even when heated. Second, attempts to prepare stereospecifically labeled deutero organozirconium derivatives result in scrambling of the 6 positions of both isomers, yielding a statistical distribution of isotopomers. The features of this scrambling process are described and a mechanism involving an organozirconium alkyl hydride species is proposed.\r\n\r\n[K(THF)2]2[U(NHAr)5] [...] THF, (Ar = 2,6-diisopropylphenyl) is prepared by treatment of Ul3(THF)4 with five equivalents of potassium 2,6-diisopropylanilide (KNHAr) in THF. Electronic absorption spectra reveal internal f-f transitions characteristic of trivalent uranium. A single crystal X-ray study revealed that the dianion is a monomer containing a trigonal bipyramidal five-coordinate uranium center. The potassium cations each interact in an [eta]6 and [eta]4 fashion with two arene rings of the arylamido ligands, and two THF molecules. Crystal data (at -70[degrees] C): Monoclinic space group P2[1]/C, with a = [...], and Z = 4.", "date": "1991", "date_type": "degree", "id_number": "CaltechETD:etd-07192007-074200", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechETD:etd-07192007-074200", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "deposited_by": "Imported from ETD-db", "deposited_on": "2007-08-02", "doi": "10.7907/qwqn-0x07", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "orcid": "0000-0002-0057-7817", "role": "chair" }, { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" }, { "id": "Schaefer-W-P", "name": { "family": "Schaefer", "given": "William P." }, "role": "member" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876", "role": "member" }, { "id": "Labinger-J-A", "name": { "family": "Labinger", "given": "Jay A." }, "orcid": "0000-0002-1942-9232", "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_submitted_date": "2007-07-19", "thesis_defense_date": "1991-04-22", "thesis_approved_date": "2007-08-02", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive\nlicense to archive and make accessible, under the conditions specified below,\nmy thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1991", "author_list": "Nelson, Janet Elizabeth", "advisor_list": "Bercaw, John E.", "comittee_list": "Grubbs, Robert H.; Bercaw, John E.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/6293", "eprint_id": 6293, "rev_number": 14, "documents": [ { "id": "/id/document/12277", "doc_id": 12277, "rev_number": 5, "files": [ { "id": "/id/file/80481", "fileid": 80481, "datasetid": "document", "objectid": 12277, "filename": "Whinnery_ll_1991.pdf", "mime_type": "application/pdf", "filesize": 2522488, "mtime": "2012-12-26 04:33:51", "url": "/6293/1/Whinnery_ll_1991.pdf" } ], "eprint_id": 6293, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": "Whinnery_ll_1991.pdf", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "final", "relation": { "items": [ { "type": "http://eprints.org/relation/hasVolatileVersion", "uri": "/id/document/27296" }, { "type": "http://eprints.org/relation/haspreviewThumbnailVersion", "uri": "/id/document/27296" }, { "type": "http://eprints.org/relation/hasVersion", "uri": "/id/document/27296" } ] } }, { "id": "/id/document/12278", "doc_id": 12278, "rev_number": 3, "files": [ { "id": "/id/file/206655", "fileid": 206655, "datasetid": "document", "objectid": 12278, "filename": "Whinnery_ll_1991.zip", "mime_type": "application/zip", "filesize": 5732053, "mtime": "2016-08-22 21:21:53", "url": "/6293/2/Whinnery_ll_1991.zip" } ], "eprint_id": 6293, "pos": 2, "format": "application/zip", "format_desc": "TIFF", "language": "en", "security": "internal", "license": "other", "main": "Whinnery_ll_1991.zip", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "final" }, { "id": "/id/document/27296", "doc_id": 27296, "rev_number": 3, "files": [ { "id": "/id/file/80479", "fileid": 80479, "datasetid": "document", "objectid": 27296, "filename": "preview.png", "mime_type": "image/png", "hash": "1445c380626854f153de9cac7450e776", "hash_type": "MD5", "filesize": 14307, "mtime": "2012-12-26 04:33:51", "url": "/6293/3/preview.png" } ], "eprint_id": 6293, "pos": 3, "placement": 3, "mime_type": "image/png", "format": "image/png", "language": "en", "security": "public", "license": "other", "main": "preview.png", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/12277" }, { "type": "http://eprints.org/relation/ispreviewThumbnailVersionOf", "uri": "/id/document/12277" }, { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/12277" } ] } }, { "id": "/id/document/126508", "doc_id": 126508, "rev_number": 1, "files": [ { "id": "/id/file/371942", "fileid": 371942, "datasetid": "document", "objectid": 126508, "filename": "indexcodes.txt", "mime_type": "text/plain", "hash": "d9c45250fdc7f9f155211fada82814f0", "hash_type": "MD5", "filesize": 26116, "mtime": "2021-06-24 00:55:15", "url": "/6293/4/indexcodes.txt" } ], "eprint_id": 6293, "pos": 4, "placement": 4, "mime_type": "text/plain", "format": "other", "format_desc": "Generate index codes conversion from application/pdf to indexcodes", "language": "en", "security": "public", "license": "other", "main": "indexcodes.txt", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/12277" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/12277" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/12277" } ] } } ], "eprint_status": "archive", "userid": 51, "dir": "disk0/00/00/62/93", "datestamp": "2011-04-13 16:58:23", "lastmod": "2021-04-16 23:10:40", "status_changed": "2011-04-13 16:58:23", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Whinnery-L-L", "name": { "family": "Whinnery", "given": "Leroy L." }, "show_email": "NO" } ] }, "title": "Synthesis, characterization and reactivity of some permethyltantalocene alkylidenes and unusually stable metallaoxetanes", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "Several tantalaoxetanes have been prepared and the X-ray crystal structure of O-exo-Cp_2*Ta(OCHPhCH_2)CH_3 is reported (Cp* = \u03b7^5-C_5Me_5). The kinetic products of the reactions of Cp_2*Ta(=CH_2)CH_3 with paraformaldehyde or benzaldehyde are O-endo-Cp_2*Ta(CH_2CH_20)CH_3 and O-endo-Cp_2*Ta(CH_2CHPhO)CH_3, respectively. These tantalaoxetanes undergo an acid and base-catalyzed isomerization to O-exo-Cp_2*Ta(OCH_2CH_2)CH_3 and O-exo-CP_2*Ta(OCHPhCH_2)CH_3 followed by thermal decomposition to Cp_2*Ta(=O)CH_3 and the appropriate olefin. Cp_2*Ta(=CH_2)H deoxygenates epoxides to form Cp_2*Ta(=O)CH_3 and olefin. No intermediates are observed in this deoxygenation under conditions where the appropriate tantalaoxetanes are stable and would have been spectroscopically observed. Stereolabeled epoxides were deoxygenated to probe the mechanism for the possible intermediacy of a 1,4-biradical. Retention of stereochemistry of the resulting olefin was observed and is indicative of a concerted mechanism. These results and their implications for the mechanism of olefin epoxidation are discussed.\r\n\r\nTreatment of Cp*_2 TaCI_2 with a variety of substituted benzyl potassium reagents affords an equilibrium mixture of CP*_2 Ta(=CHC_6H_5)H, 1, and Cp*_2 Ta(o-CH_2C_6H_4)H, 2, which interconvert presumably via the unstable 16 electron intermediate [Cp*_2Ta(CH_2C_6H_5)]. Several derivatives substituted at the phenyl ring have been prepared to explore the effect of both sterics and electronics on the a-hydrogen migration equilibrium. Trapping of the benzyl intermediate by methylenetrialkylphosphoranes results in methylene transfer to give Cp*_2 Ta(=CH_2)CH_2C_6H_5. The substituted benzyl derivatives have provided a system to determine the influence of phenyl sUbstituents on migratory aptitude of the benzyl group.\r\n", "date": "1991", "date_type": "degree", "id_number": "CaltechTHESIS:04112011-130949006", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:04112011-130949006", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "deposited_by": "Tony Diaz", "deposited_on": "2011-04-13 16:58:23", "doi": "10.7907/s4x8-zb56", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "name": { "family": "Unknown", "given": "Unknown" } } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1990-09-20", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1991", "author_list": "Whinnery, Leroy L.", "advisor_list": "Bercaw, John E.", "comittee_list": "Unknown, Unknown" }, { "id": "https://thesis.library.caltech.edu/id/eprint/2546", "eprint_id": 2546, "rev_number": 14, "documents": [ { "id": "/id/document/4805", "doc_id": 4805, "rev_number": 4, "files": [ { "id": "/id/file/27790", "fileid": 27790, "datasetid": "document", "objectid": 4805, "filename": "Barner_cj_1990.pdf", "mime_type": "application/pdf", "filesize": 3466421, "mtime": "2012-12-26 02:52:29", "url": "/2546/1/Barner_cj_1990.pdf" } ], "eprint_id": 2546, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "format_desc": "Original (no OCR) Barner_cj_1990.pdf", "language": "en", "security": "internal", "license": "other", "main": "Barner_cj_1990.pdf", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "final", "relation": { "items": [ { "type": "http://eprints.org/relation/hasVolatileVersion", "uri": "/id/document/21357" }, { "type": "http://eprints.org/relation/haspreviewThumbnailVersion", "uri": "/id/document/21357" }, { "type": "http://eprints.org/relation/hasVersion", "uri": "/id/document/21357" } ] } }, { "id": "/id/document/21357", "doc_id": 21357, "rev_number": 3, "files": [ { "id": "/id/file/27788", "fileid": 27788, "datasetid": "document", "objectid": 21357, "filename": "preview.png", "mime_type": "image/png", "hash": "2710dea67bb2f27697b4333bc0eb10ff", "hash_type": "MD5", "filesize": 11544, "mtime": "2012-12-26 02:52:29", "url": "/2546/2/preview.png" } ], "eprint_id": 2546, "pos": 2, "placement": 2, "mime_type": "image/png", "format": "image/png", "language": "en", "security": "public", "license": "other", "main": "preview.png", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/4805" }, { "type": "http://eprints.org/relation/ispreviewThumbnailVersionOf", "uri": "/id/document/4805" }, { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/4805" } ] } }, { "id": "/id/document/135747", "doc_id": 135747, "rev_number": 2, "files": [ { "id": "/id/file/388519", "fileid": 388519, "datasetid": "document", "objectid": 135747, "filename": "barner-cj_1990.pdf", "mime_type": "application/pdf", "hash": "471cd48824e7df75cadd769addb5fab3", "hash_type": "MD5", "filesize": 2967741, "mtime": "2022-01-18 21:45:06", "url": "/2546/3/barner-cj_1990.pdf" } ], "eprint_id": 2546, "pos": 3, "placement": 3, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": "barner-cj_1990.pdf", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "final" }, { "id": "/id/document/135749", "doc_id": 135749, "rev_number": 1, "files": [ { "id": "/id/file/388525", "fileid": 388525, "datasetid": "document", "objectid": 135749, "filename": "indexcodes.txt", "mime_type": "text/plain", "hash": "bc032c93bc4c894bd2dc168bcdf33590", "hash_type": "MD5", "filesize": 25616, "mtime": "2022-01-18 22:25:19", "url": "/2546/4/indexcodes.txt" } ], "eprint_id": 2546, "pos": 4, "placement": 4, "mime_type": "text/plain", "format": "other", "format_desc": "Generate index codes conversion from application/pdf to indexcodes", "language": "en", "security": "public", "license": "other", "main": "indexcodes.txt", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/135747" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/135747" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/135747" } ] } } ], "eprint_status": "archive", "userid": 2, "dir": "disk0/00/00/25/46", "datestamp": "2007-06-28", "lastmod": "2022-01-18 22:18:58", "status_changed": "2009-09-25 02:40:09", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Barner-Claudia-Jane", "name": { "family": "Barner", "given": "Claudia Jane" }, "show_email": "NO" } ] }, "title": "Part I. Coordination Chemistry of High-Valent Osmium Polyanionic Chelating Ligand Complexes with Imine, Imido and Nitrido Ligands. Part II. Asymmetric Hydrogenation Using a Resolved Chiral Scandium Hydride Complex", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "Part I: The chemistry of high-valent osmium polyanionic chelating ligand complexes with imine, imido and nitrido ligands is explored. The synthesis and x-ray diffraction study of Os(\u03b7\u2074-HBA-B)(NC\u2086H\u2085NHC\u2086H\u2084) is reported. A neutral, octahedral Os(VIII) intermediate complex is postulated. The synthesis and x-ray diffraction study of [OsN(\u03b7\u2074-HBA-B)]- is reported. The mechanism of formation is discussed. These complexes represent two of the first examples of non-planar amide ligands in transition metal chemistry. The synthesis of a five-coordinate imido complex, Os(N-C\u2081\u2080 H\u2081\u2086), is reported. The formation of the first osmium-osmium quadruply-bonded complex, [Os(\u03b7\u2074-HBA-B)]\u2082, is reported. Reactions with the nitrido complex, [OsN(\u03b7\u2074-HBA-B)]\u207b,and the methylimido complex, OsNMe(\u03b7\u2074-HBA-B), are also reported.
\r\n\r\nPart II: The asymmetric hydrogenation of the prochiral substrate, methylene indane, is induced by the resolved chiral scandium complex, Me\u2082Si(\u03b7\u2075-C\u2085Me\u2084)(\u03b7\u2075-(C\u2085H\u2083(1R,2R,5S)-menthyl)ScH, in substoichiometric quantities. Methylene indane is hydrogenated to produce methylindane with an enantiomeric excess of 34% and a maximum turnover of four.
", "date": "1990", "date_type": "degree", "id_number": "CaltechETD:etd-06112007-095040", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechETD:etd-06112007-095040", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "ARCS Foundation" }, { "agency": "Caltech" }, { "agency": "W. R. Grace Fellowship" } ] }, "collection": "CaltechTHESIS", "reviewer": "Melissa Ray", "deposited_by": "Imported from ETD-db", "deposited_on": "2007-06-28", "doi": "10.7907/tj33-3482", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "orcid": "0000-0002-0057-7817", "role": "chair" }, { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" }, { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876", "role": "member" }, { "id": "McKoy-B-V", "name": { "family": "McKoy", "given": "Basil Vincent" }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_submitted_date": "2007-06-11", "thesis_defense_date": "1989-09-25", "thesis_approved_date": "2007-06-28", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive\nlicense to archive and make accessible, under the conditions specified below,\nmy thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1990", "author_list": "Barner, Claudia Jane", "advisor_list": "Bercaw, John E.", "comittee_list": "Grubbs, Robert H.; Bercaw, John E.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/2018", "eprint_id": 2018, "rev_number": 19, "documents": [ { "id": "/id/document/3567", "doc_id": 3567, "rev_number": 4, "files": [ { "id": "/id/file/21066", "fileid": 21066, "datasetid": "document", "objectid": 3567, "filename": "Bunel_ee_1989.pdf", "mime_type": "application/pdf", "filesize": 2717042, "mtime": "2012-12-26 02:45:38", "url": "/2018/1/Bunel_ee_1989.pdf" } ], "eprint_id": 2018, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "format_desc": "Original (no OCR) Bunel_ee_1989.pdf", "language": "en", "security": "internal", "license": "other", "main": "Bunel_ee_1989.pdf", 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"media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/107400" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/107400" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/107400" } ] } } ], "eprint_status": "archive", "userid": 2, "dir": "disk0/00/00/20/18", "datestamp": "2007-05-24", "lastmod": "2020-12-18 02:11:02", "status_changed": "2009-09-25 02:23:25", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "ebunel@anl.gov", "id": "Bunel-Emilio-Enrique", "name": { "family": "Bunel", "given": "Emilio Enrique" }, "show_email": "YES" } ] }, "title": "Synthetic and Mechanistic Studies of Organoscandium Compounds. Dimerization and Branching of Alkenes Catalyzed by Scandocene Hydrides", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "Mixed-ring scandocene alkyl and hydride derivatives of structure Cp*CpSc(CH\u2083)(PMe\u2083), Cp*CpSc(\u03b7\u00b9-\u03b7\u2075-C\u2085H\u2084(Cp*Sc(H), Cp*(\u03b7\u2075-1,3,4-C\u2085Me\u2083H\u2082)Sc(CH\u2083)(PMe\u2083), and Cp*(\u03b7\u2075-1,3,4-C\u2085Me\u2083H\u2082)Sc(H)(PMe\u2083) were prepared (Cp* = \u03b7\u2075-C\u2085Me\u2085, Cp = \u03b7\u2075-C\u2085H\u2085. Dimethylsilicon bridged scandocene alkyl and hydride derivatives Me\u2082Si(\u03b7\u2075-C\u2085Me\u2084)\u2082ScCH(SiMe\u2083)\u2082, Me\u2082Si(\u03b7\u2075-C\u2085Me\u2084)\u2082Sc(H)(PMe\u2083), meso-Me\u2082Si(\u03b7\u2075-t-butylC\u2085H\u2083)\u2082ScCH\u2082SiMe\u2083, and (meso-Me\u2082Si(\u03b7\u2075-t-butylC\u2085H\u2083)\u2082Sc(H))\u2082 were also prepared. The activation energy for phosphine dissociation in Cp*CpSc(CH\u2083)(PMe\u2083) and Cp*(\u03b7\u2075-1,3,4-C\u2085Me\u2083H\u2082)Sc(H)(PMe\u2083) were measured. The crystal structures of Me\u2082Si(\u03b7\u2075-C\u2085Me\u2084)\u2082ScCH(SiMe\u2083)\u2082 and Me\u2082Si(\u03b7\u2075-C\u2085Me\u2084)\u2082Sc(H)(PMe\u2083) were determined.
\r\n\r\nThe hydride derivatives, Me\u2082Si(\u03b7\u2075-C\u2085Me\u2084)\u2082Sc(H)(PMe\u2083) and (meso-Me\u2082Si(\u03b7\u2075-t-butylC\u2085H\u2083)\u2082Sc(H))\u2082 catalyze the following carbon-carbon bond forming reactions: (1) The catalytic dimerization of \u03b1-olefins to head-to-tail dimers, (2) The catalytic cyclization of \u03b1, \u03c9-diolefins to methylenecycloalkanes with ring sizes between 5 and 9 carbon atoms, (3) The catalytic formation of six-membered ring nitrogen and sulfur heterocycles by catalytic cyclization of bisallyl amines and bisallyl sulfides respectively and (4) The catalytic formation of the spiro hydrocarbons 2-methylene spiro[4.4] nonane and 2-methylene dispiro [4.1.4.2] tridecane by catalytic cyclization of 5-methylene-1,8-nonadiene and 5,8-dimethylene-1,11-dodecadiene.
\r\n\r\n(meso-Me\u2082Si(\u03b7\u2075-t-butylC\u2085H\u2083)\u2082Sc(H))\u2082 catalyzes the ring opening reaction of methylenecyclopropane to butadiene and methylenecyclobutane to 1,4-pentadiene. Labelling experiments show that intramolecular olefin insertion in \u03c9-alkenyl scandium complexes and \u03b2-alkyl elimination in cycloalkylmethyl scandium complexes is reversible when rings containing 3 or 4 carbon atoms are involved. The hydride derivative (meso-Me\u2082Si(\u03b7\u2075-t-butylC\u2085H\u2083)\u2082Sc(H))\u2082 also catalyzes the isomerization of 1,4-pentadiene to isoprene and 2-methyl-1,4-pentadiene to 2,3-dimethylbutadiene and the isomerization of 3-methyl-1,4-pentadiene to 1,5-hexadiene, which is then cyclized to methylenecyclopentane.
", "date": "1989", "date_type": "degree", "id_number": "CaltechETD:etd-05242007-075254", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechETD:etd-05242007-075254", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Melissa Ray", "deposited_by": "Imported from ETD-db", "deposited_on": "2007-05-24", "doi": "10.7907/3HDJ-ST65", "alt_title": { "items": [ "Synthetic and Mechanistic Studies of Organoscandium Compounds", "Dimerization and Branching of Alkenes Catalyzed by Scandocene Hydrides" ] }, "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "chair" }, { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" }, { "id": "Schaefer-W-P", "name": { "family": "Schaefer", "given": "William P." }, "role": "member" }, { "id": "Myers-A-G", "name": { "family": "Myers", "given": "Andrew G." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_submitted_date": "2007-05-24", "thesis_defense_date": "1988-06-01", "thesis_approved_date": "2007-05-24", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive\nlicense to archive and make accessible, under the conditions specified below,\nmy thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1989", "author_list": "Bunel, Emilio Enrique", "advisor_list": "Bercaw, John E.", "comittee_list": "Gray, Harry B.; Bercaw, John E.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/7935", "eprint_id": 7935, "rev_number": 23, "documents": [ { "id": "/id/document/42796", "doc_id": 42796, "rev_number": 3, "files": [ { "id": "/id/file/127961", "fileid": 127961, "datasetid": "document", "objectid": 42796, "filename": "Trimmer_ms_1989.pdf", "mime_type": "application/pdf", "hash": "667f7b3c4a57c2befc8da893769a389b", "hash_type": "MD5", "filesize": 25187602, "mtime": "2013-08-23 18:16:47", "url": "/7935/1/Trimmer_ms_1989.pdf" } ], "eprint_id": 7935, "pos": 1, "placement": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": 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"media_sample_start": "0", "media_sample_stop": "0", "content": "archival" } ], "eprint_status": "archive", "userid": 87, "dir": "disk0/00/00/79/35", "datestamp": "2013-08-26 14:41:11", "lastmod": "2021-12-22 23:58:50", "status_changed": "2013-08-26 14:41:11", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Trimmer-Mark-S", "name": { "family": "Trimmer", "given": "Mark S." }, "show_email": "NO" } ] }, "title": "Mechanistic and Reactivity Studies of Bent Metallocene Complexes of Niobium and Tantalum", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "A variety of olefin hydride complexes of niobium and tantalum has been prepared in order to study their reactivity and to gain insight into organometallic reaction mechanisms. Examination of a series of ethylene and propylene complexes of niobocene (Cp\u2082Nb; Cp = \u03b7\u2075-C\u2085H\u2085), permethylniobocene (Cp*\u2082Nb; Cp* = \u03b7\u2075-C\u2085(CH\u2083)\u2085), tantalocene, and permethyltantalocene has indicated that there are both large electronic and steric effects deriving from the metal (and its ancillary ligands) in the olefin insertion (\u03b2-migratory insertion) process. Furthermore, a thermodynamic and kinetic analysis has been completed for a series of substituted styrene complexes of niobocene in order to better understand the important electronic properties of the olefin. The results are in accord with a concerted four-center process with only moderate charge development.
\r\n\r\nThe special case of \u03b2-migratory insertion of a hydride ligand into coordinated benzyne has also been studied for the permethyltantalocene system. The coordinatively unsaturated (sixteen electron) phenyl tautomer, which is made accessible by the facile benzyne hydride insertion reaction, readily reacts with a variety of ligands, L, to afford Cp*\u2082 Ta(C\u2086H\u2085)L complexes (L = CO, O\u2082, NC\u2261R, :CH\u2082, H\u2082, etc.). This family of compounds exhibits interesting reactivity (a-migratory insertion, O\u2082 activation, and reductive elimination) which is discussed in some detail.
\r\n\r\nFinally a series of paramagnetic seventeen electron Cp*\u2082 TaX\u2082 (X = halide, alkyl, hydride) complexes, and the corresponding cationic and anionic species, have been prepared and studied. The odd electron neutral complexes exhibit surprising thermal stability and undergo very little reactivity. While the chemistry of the anionic compounds is almost completely dominated by their potent reducing power, that of the cations is quite diverse and amenable for study. Therefore the syntheses and reactivity (1,2-eliminations, ligand insertions, and deprotonation reactions) of these coordinatively unsaturated sixteen electron species are presented.
", "date": "1989", "date_type": "degree", "id_number": "CaltechTHESIS:08232013-111400988", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:08232013-111400988", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Department of Energy (DOE)", "grant_number": "DE-FG03-85ER13431" }, { "agency": "NSF", "grant_number": "CHE-8303735" }, { "agency": "Shell Companies Foundation" }, { "agency": "NSF", "grant_number": "CHE-84-40137" }, { "agency": "BP America" } ] }, "collection": "CaltechTHESIS", "reviewer": "Tony Diaz", "deposited_by": "Benjamin Perez", "deposited_on": "2013-08-26 14:41:11", "doi": "10.7907/bads-b915", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876", "role": "chair" }, { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" }, { "email": "chans@its.caltech.edu", "id": "Chan-S-I", "name": { "family": "Chan", "given": "Sunney I." }, "orcid": "0000-0002-5348-2723", "role": "member" }, { "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "orcid": "0000-0002-0057-7817", "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1988-09-08", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. 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"license": "other", "main": "st-clair-m_1989.zip", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "archival" } ], "eprint_status": "archive", "userid": 87, "dir": "disk0/00/00/79/41", "datestamp": "2013-08-26 17:22:19", "lastmod": "2021-10-26 21:37:00", "status_changed": "2013-08-26 17:22:19", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "mstclair@coe.edu", "id": "St-Clair-Martin-A", "name": { "family": "St. Clair", "given": "Martin A." }, "show_email": "YES" } ] }, "title": "Synthetic and Structural Studies of Permethylscandocene and Permethyltantalocene Derivatives", "ispublished": "unpub", "full_text_status": "public", "keywords": "Scandium, tantalum, carbon monoxide activation", "abstract": "Cp*\u2082Sc-H reacts with H\u2082 and CO at -78\u00b0C to yield Cp*\u2082ScOCH\u2083. A stepwise reduction of CO to an alkoxide is observed when CO reacts with Cp*\u2082ScC\u2086H\u2084CH\u2083-p to give the \u03b7\u00b2-acyl Cp*\u2082Sc(CO)C\u2086H\u2084CH\u2083-p, which then reacts with H\u2082 to produce Cp*\u2082ScOCH\u2082C\u2086H\u2084CH\u2083-p. Cp*\u2082ScCH\u2083 and Cp*\u2082ScH(THF) react with CO to give uncharuncharacterizable products. Cp*\u2082ScH and Cp*\u2082ScCH\u2083 react with Cp\u2082MCO (M = Mo, W) to give scandoxycarbenes, Cp\u2082M=C(CH\u2083)OScCp*\u2082, while a wide variety of Cp*\u2082ScX (X = H, CH\u2083, N(CH\u2083)\u2082, CH\u2082CH\u2082C\u2086H\u2085) reacts with CpM(CO)\u2082 (M = Co, Rh) to yield similar carbene complexes. An x-ray crystal structure determination of Cp(CO)Co=C(CH\u2083)-OScCp*\u2082 revealed a \u00b5\u00b2: \u03b7\u00b9, \u03b7\u00b9 carbonyl interaction between the Co-CO and Sc.
\r\n\r\nCO\u2082 inserts cleanly into Sc-phenyl bonds at -78\u00b0C to produce a carboxylate complex, Cp*\u2082Sc(O\u2082C)C\u2086H\u2084CH\u2083-p. The structure of this compound was determined by x-ray crystallographic techniques.
\r\n\r\nExcess C\u2082H\u2082 reacts with Cp*\u2082ScR (R = H, alkyl, aryl, alkenyl, alkynyl, amide) at temperatures below -78\u00b0C to form the alkynyl species Cp*\u2082Sc-C\u2261C-H, which then reacts with the remaining acetylene to form polyacetylene. Cp*\u2082Sc-C\u2261C-H further reacts to yield Cp*\u2082Sc-C\u2261C-ScCp*\u2082. This unusual C\u2082 bridged dimer was characterized by x-ray crystallography.
\r\n\r\nAttempts were made to model the C-N bond breaking step of hydrodenitrogenation by synthesizing Cp*\u2082TaH(\u03b7\u00b2-H\u2082C=N(C\u2086H\u2084X)) and studying its rearrangement to Cp*\u2082Ta(=N(C\u2086H\u2084X))(CH\u2083). The 1,2 addition/elimination reactions of Cp*\u2082Ta(\u03b7\u00b2-H\u2082C=N(CH\u2083)H and Cp*\u2082Ta(=X)H (X=O, S, NH, N(C\u2086H\u2085)) were investigated. Cp*\u2082Ta(=NH)H was found to react with D\u2082 to give Cp*\u2082Ta(=ND)H, implying a nonsymmetric amide-dihydride intermediate for the addition/elimination process. Cp*\u2082Ta(=S)H and H\u2082O equilibrate with Cp*\u2082Ta(=O)H and H\u2082S, which allowed determination of the difference in bond strengths for Ta=O and Ta=S. Ta=O was found to be approximately 41 kcals/mole stronger than Ta=S.
", "date": "1989", "date_type": "degree", "id_number": "CaltechTHESIS:08262013-094527536", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:08262013-094527536", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" }, { "agency": "Department of Energy (DOE)" }, { "agency": "Shell Companies Foundation" } ] }, "collection": "CaltechTHESIS", "reviewer": "Tony Diaz", "deposited_by": "Benjamin Perez", "deposited_on": "2013-08-26 17:22:19", "doi": "10.7907/192V-TK10", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "chair" }, { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876", "role": "member" }, { "id": "Schaefer-W-P", "name": { "family": "Schaefer", "given": "William P." }, "role": "member" }, { "email": "rhg@caltech.edu", "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "orcid": "0000-0002-0057-7817", "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1989-02-22", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1989", "author_list": "St. Clair, Martin A.", "advisor_list": "Bercaw, John E.", "comittee_list": "Bercaw, John E.; Gray, Harry B.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/7403", "eprint_id": 7403, "rev_number": 38, "documents": [ { "id": "/id/document/34734", "doc_id": 34734, "rev_number": 3, "files": [ { "id": "/id/file/110069", "fileid": 110069, "datasetid": "document", "objectid": 34734, "filename": "Bulls_ar_1988.pdf", "mime_type": "application/pdf", "hash": "0b779cc2607693695188521ce8fa8002", "hash_type": "MD5", "filesize": 29401451, "mtime": "2013-01-18 16:43:29", "url": "/7403/3/Bulls_ar_1988.pdf" } ], "eprint_id": 7403, "pos": 3, "placement": 3, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": 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\r\n\r\nThermal decomposition of Cp*2Hf(CH2C6H5)2 (Cp* = (\u03b75-C5Me5)) in benzene-d6\r\ncleanly affords toluene and hafnabenzocyclobutene [chemical symbol; see abstract in scanned thesis for details]. Deuterium\r\nlabeling of the benzyl ligands indicates that decomposition of Cp*2Hf(CY2C6H5)2 (Y = H, D)\r\nproceeds primarily by \u03b1-H abstraction to form a permethylhafnocene benzylidene\r\nintermediate [Cp*2Hf=CHC6H5], which rapidly rearranges to the\r\nmetallated-cyclopentadienyl, or \"tucked-in\" benzyl complex\r\nCp*(\u03b75,\u03b71-C5Me4CH2)HfCH2C6H5. The observed product arises from rearrangement of\r\nCp*(\u03b75,\u03b71-C5Me4CH2)HfCH2C6H5 to its tautomer [chemical symbol; see abstract in scanned thesis for details]. A series of meta\r\nsubstituted benzyl derivatives of the proposed metallated cyclopentadienyl intermediates,\r\nCp*(\u03b75,\u03b71-C5Me4CH2)HfCH2C6H4X (X = H, CH3, CF3, NMe2), has therefore been prepared.\r\nThe kinetics of their conversion to [chemical symbol; see abstract in scanned thesis for details] have been examined in order to\r\nprobe the nature of the transition state for aryl C-H bond activation which occurs in the final\r\nsteps of the rearrangement. The rates are found to be insensitive to the nature of X,\r\nsuggesting that the benzyl \u03c0 system is not attacked by the electrophilic hafnium center along\r\nthe reaction coordinate for C-H bond activation. The structure of\r\nCp*(\u03b75,\u03b71-C5Me4CH2)HfCH2C6H5, as determined by single crystal X-ray diffraction\r\ntechniques, indicates that the complex is best described as a Hf(IV) derivative containing an\r\n\u03b75,\u03b71-C5Me4CH2 Iigand, rather than a Hf(ll) \u03b76-fulvene adduct.\r\nCp*(\u03b75,\u03b71-C5Me4CH2)HfCH2C6H5 crystallizes in the triclinic space group P1̅ (a= 9.084(2), b\r\n= 10.492(2), c = 12.328(1) \u00c5; \u03b1 = 95.81(1), \u03b2 = 96.60(1), \u03b3 = 91.15(2); Z = 2). Least-squares\r\nrefinement led to a value for R of 0.048 (I > 3\u03c3I) and a goodness-of-fit of 4.37 for 4029\r\nindependent reflections.
\r\n\r\nChapter 2
\r\n\r\nThermolysis of the singly metallated complex\r\nCp*(\u03b75,\u03b71-C5Me4CH2)Hf(CH2CMe3) in toluene affords neopentane and the doubly\r\nmetallated complex Cp*(\u03b75,\u03b71,\u03b71-C5Me3(CH2)2)Hf. The structure of\r\nCp*(\u03b75,\u03b71,\u03b71-C5Me3(CH2)2)Hf, as determined by single-crystal X-ray diffraction\r\ntechniques, confirms that metallation has occurred at adjacent methyl groups of the same\r\npentamethylcyclopentadienyl ring. Cp*(\u03b75,\u03b71,\u03b71-C5Me3(CH2)2)Hf crystallizes in the space\r\ngroup P2/c (a= 13.775(4) \u00c5, b = 9.516(1) \u00c5, c = 14.183(6) \u00c5; \u03b2 = 103.965(31)\u00b0, z = 4). Least\r\nsquares refinement led to a value for R of 0.036 (I > 3\u03c3i) and a goodness-of-fit of 2.66 for\r\n1984 independent reflections. Cp*(\u03b75,\u03b71,\u03b71-C5Me3(CH2)2)Hf and Cp*(\u03b75,\u03b71-C5Me4CH2)Hfl\r\ncleanly insert one equivalent of ethylene into the hafnium methylene carbon bond to form\r\nthe propyl bridged species Cp*(\u03b75,\u03b71,\u03b71-C5Me3(CH2)(CH2CH2CH2))Hf and\r\nCp*(\u03b75,\u03b71-C5Me3CH2CH2CH2)Hfl, respectively.\r\nCp*(\u03b75,\u03b71,\u03b71-C5Me3(CH2)(CH2CH2CH2))Hf reacts with excess ethylene to cleanly afford\r\n[chemical symbol; see abstract in scanned thesis for details]. Deuterium labeling experiments suggest that\r\nthis reaction occurs via an \u03b1-H abstraction to generate the alkylidene intermediate\r\nCp*(\u03b75,\u03b71-C5Me4CH2CH2CH=)Hf, which rapidly traps ethylene to form the observed\r\nproduct. The metallated phenyl complex Cp*(\u03b75,\u03b71-C5Me3CH2)HfC6H5 has been shown to\r\nbe in equilibrium with the benzyne complex Cp*2Hf(\u03b72-C6H4). Heating benzene-d6\r\nsolutions of Cp*(\u03b75,\u03b71-C5Me3CH2)HfC6H5 in the presence of ethylene traps the benzyne\r\nintermediate and generates the hafnacyclopentene [chemical symbol; see abstract in scanned thesis for details].
\r\n\r\nChapter 4
\r\n\r\nRelative bond dissociation energies (BDEs) have been obtained by equilibrating\r\nearly transition metal alkyls and hydrides with H2 or the C-H bonds of hydrocarbons. Thus,\r\nin benzene solution Cp*2HfH2 (Cp* = (\u03b75-C5Me5)) equilibrates with Cp*2Hf(C6H5)H and\r\ndihydrogen. From the enthalpy of the reaction, \u0394H\u00b0 = +6.0(3), the Hf-H (BDE) is calculated\r\nto be 0.8(3) kcal\u00b7mol-1 stronger than the Hf-C6H5 BDE. Relative Sc-C6H5 and Sc-alkyl\r\nBDEs have been estimated from the equilibration of the metallated complex\r\nCp*(\u03b75,\u03b71-C5Me4CH2CH2CH2)Sc, C6H6 and Cp*(\u03b75-C5Me4CH2CH2CH3)Sc(C6H5), the\r\nSc-C6H5 BDE being 16.6(3) kcal\u00b7mol-1 stronger than the Sc-CH2CH2CH2C5Me4 BDE. From\r\na similar reversible intramolecular metallation of Cp*(\u03b75-C5Me4CH2CH2CH3)HfH2 to give\r\nCp*(\u03b75,\u03b71-C5Me4CH2CH2CH2)HfH and dihydrogen, the Hf-H BDE is estimated to be 23.0(3)\r\nkcal\u00b7mol-1 stronger than the Hf-CH2CH2CH2C5Me4 BDE. The equilibration of\r\nCp*(\u03b75-C5Me4CH2C6H5)Sc-C\u2261CCMe3 with the metallated scandocene derivative\r\nCp*(\u03b75,\u03b71-C5Me4CH2-o-C6H4)Sc and tert-butylacetylene lies very far towards\r\nCp*(\u03b75-C5Me4CH2C6H5)Sc-C\u2261CCMe3, so that only a lower limit for the relative Sc-alkynyl\r\nand Sc-aryl BDEs may be determined: BDE(Sc-alkynyl) - BDE(Sc-aryl) \u2265 29(5) kcal\u00b7mol-1.\r\nThese early transition metal-hydrocarbyl (M-R) BDEs correlate with the corresponding H-R\r\nBDEs (i.e. M-alkynyl > M-aryl > M-alkyl); however, the M-R BDEs increase more rapidly with\r\ns character than does the H-R BDEs. The origin of this effect is not known, but it is\r\nundoubtedly also responsible for the characteristically high M-H BDEs for transition metal\r\nhydride compounds. In an effort to probe the polarity of Sc-aryl bonds a series of\r\nscandocene derivatives capable of reversibly metallating at either of two differently\r\nsubstituted benzyl groups was prepared. The equilibrium constants for these metallated\r\nderivatives: (\u03b75,\u03b71-C5Me4CH2-o-C6H3-p-X)(\u03b75-C5Me4CH2C6H4-m-CH3)Sc \u21cc\r\n(\u03b75-C5Me4CH2C6H4-m-X)(\u03b75,\u03b71- C5Me4CH2-o-C6H3-p-CH3)Sc (X= H, CF3, NMe2) were\r\ndetermined. The small dependence of Keq on the nature of X suggests that the Sc-aryl\r\nbond is essentially covalent with only a slight ionic character.
", "date": "1988", "date_type": "degree", "id_number": "CaltechTHESIS:01172013-130132630", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:01172013-130132630", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Tony Diaz", "deposited_by": "Benjamin Perez", "deposited_on": "2013-01-18 17:20:02", "doi": "10.7907/ZSJW-KC36", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "chair" }, { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" }, { "id": "Schaefer-W-P", "name": { "family": "Schaefer", "given": "William P." }, "role": "member" }, { "email": "jlbchamp@caltech.edu", "id": "Beauchamp-J-L", "name": { "family": "Beauchamp", "given": "Jesse L." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1987-08-17", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1988", "author_list": "Bulls, Al Ray", "advisor_list": "Bercaw, John E.", "comittee_list": "Gray, Harry B.; Bercaw, John E.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/203", "eprint_id": 203, "rev_number": 17, "documents": [ { "id": "/id/document/306", "doc_id": 306, "rev_number": 4, "files": [ { "id": "/id/file/1929", "fileid": 1929, "datasetid": "document", "objectid": 306, "filename": "Burger_bj_1987.pdf", "mime_type": "application/pdf", "filesize": 5144183, "mtime": "2012-12-26 02:28:01", "url": "/203/1/Burger_bj_1987.pdf" } ], "eprint_id": 203, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "format_desc": "Burger_bj_1987.pdf", "language": "en", "security": "public", "license": "other", "main": "Burger_bj_1987.pdf", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "final", "relation": { "items": [ { "type": "http://eprints.org/relation/hasVolatileVersion", "uri": "/id/document/17131" }, { "type": "http://eprints.org/relation/haspreviewThumbnailVersion", "uri": "/id/document/17131" }, { "type": "http://eprints.org/relation/hasVersion", "uri": "/id/document/17131" } ] } }, { "id": "/id/document/17131", "doc_id": 17131, "rev_number": 2, "files": [ { "id": "/id/file/1927", "fileid": 1927, "datasetid": "document", "objectid": 17131, "filename": "preview.png", "mime_type": "image/png", "hash": "219f713ea44f38eb5d4cdc428c93e916", "hash_type": "MD5", "filesize": 8376, "mtime": "2012-12-26 02:28:01", "url": "/203/2/preview.png" } ], "eprint_id": 203, "pos": 2, "placement": 2, "mime_type": "image/png", "format": "image/png", "language": "en", "security": "public", "license": "other", "main": "preview.png", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/306" }, { "type": "http://eprints.org/relation/ispreviewThumbnailVersionOf", "uri": "/id/document/306" }, { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/306" } ] } } ], "eprint_status": "archive", "userid": 2, "dir": "disk0/00/00/02/03", "datestamp": "2008-01-16", "lastmod": "2021-07-22 17:43:10", "status_changed": "2009-09-25 01:31:03", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "bjburger@chevron.com", "id": "Burger-Barbara-J", "name": { "family": "Burger", "given": "Barbara J." }, "show_email": "NO" } ] }, "title": "Olefin Insertion and \u03b2-Elimination Reactions of Permethylniobocene Olefin Hydride and Permethylscandocene Alkyl Complexes", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "Permethylniobocene styrene hydride complexes, Cp*2Nb(CH2=CHC6H4-m-X)H (Cp* = C5Me5, X = CH3, NMe2, CF3) have been prepared and their rates of olefin insertion measured by coalescence techniques. The rates compare favorably with those measured for the analogous para-substituted complexes, suggesting that electronic effects in the transition state are largely inductive in nature. The crystal structure of Cp*2Nb(CH2=CHC6H5)H was determined. The phenyl ring of the styrene is twisted out of resonance with the olefin to avoid unfavorable steric interactions with the bulky Cp* rings.
\r\n\r\nThe rates of ethylene insertion in the Sc-C bond for Cp*2ScR (R = CH3, CH2CH3, CH2CH2CH3 have been measured at low temperature by 13C NMR; the second order rate constants (M-1 sec-1, -80\u00b0C. The slow rate for the ScCH2CH3 complex is attributed to a ground state stabilization by a \u03b2-C-H interaction.
\r\n\r\nThe \u03b2-hydrogen elimination rates for a series of permethylscandocene alkyl complexes Cp*2ScCH2CH2R (R = H, CH3, CH2CH3, SiMe3, C6H5, C6H4-p-CH3, C6H4-p-CF3, and C6H4-p-NMe2) were measured by trapping kinetics. A transition state for the \u03b2-hydrogen elimination was proposed where there is a partial positive charge on the \u03b2-carbon and the hydrogen is transferred to the scandium center as H-.
\r\n\r\n[Cp*2ScH] catalyses the ring opening of methylenecyclopropane and methylenecyclobutane. The ring opening (\u03b2-alkyl elimination) is reversible in the case of methylenecyclobutane. Addition of one equivalent of methylenecyclopentane to [Cp*2ScH] results in the formation of the scandium cyclopentylmethyl complex. This complex undergoes preferential \u03b2-alkyl (reversibly) over \u03b2-hydrogen elimination due to the unfavorable steric congestion encountered in the transition state of the latter.
\r\n\r\n[Cp*2ScH] reacts rapidly at -80\u00b0C with ethyl vinyl ether and vinylfluoride to generate an equimolar mixture of the Cp*2ScX(X = OEt, F, respectively) and Cp*2ScCH2CH3. No intermediates are seen in these reactions and two mechanisms, one involving a \u03b2-X ethyl intermediate and one invoking direct \u03c3-bond metathesis are proposed to account for the products. With vinyldiphenylphosphine, the initial product of insertion, Cp*2ScCH2CH2PPh2 is stable at low temperature; upon warming, this complex undergoes \u03b2-PPh2 elimination.
", "date": "1987", "date_type": "degree", "id_number": "CaltechETD:etd-01162008-111854", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechETD:etd-01162008-111854", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Shell Oil Company" } ] }, "collection": "CaltechTHESIS", "reviewer": "Melissa Ray", "local_group": { "items": [ "Caltech Distinguished Alumni Award" ] }, "deposited_by": "Imported from ETD-db", "deposited_on": "2008-01-16", "doi": "10.7907/BJEC-TH82", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "chair" }, { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" }, { "id": "Marsh-R-E", "name": { "family": "Marsh", "given": "Richard Edward" }, "role": "member" }, { "email": "jlbchamp@caltech.edu", "id": "Beauchamp-J-L", "name": { "family": "Beauchamp", "given": "Jesse L." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_submitted_date": "2008-01-16", "thesis_defense_date": "1987-05-04", "thesis_approved_date": "2008-01-16", "thesis_awards": "Caltech Distinguished Alumni Award, 2021", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive\nlicense to archive and make accessible, under the conditions specified below,\nmy thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation or project report. 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Synthetic routes which allow systematic variation of metal (Ru, Fe), phosphines (PMe3, PEt3, PnBu3, PMe2Ph, DMPE), and sigma-bonded ligands (halide, hydride, alkyl, heteroatom) have been developed.
\r\n\r\nThermally and photochemically induced ligand loss from these complexes has been studied. Trapping and C-H bond activation chemistry have been observed for the transient [Cp*(PR3)MX] complexes produced upon ligand loss. The reactivity of analogous ruthenium and iron complexes is compared and discussed.
\r\n\r\nThe Ru(IV) complex, Cp*(PMe3)RuH3, has been prepared and isolated. This complex is found to catalyze H-D exchange, and hydrogenations of unsaturated organic species. The analogous Fe(IV) complex, Cp*(PMe3)FeH3, has been prepared and observed spectroscopically. Hydrogen bonding modes in these polyhydrides are discussed. Highly fluxional Cp*(PMe3)FeH3 is proposed to be in equilibrium with Cp*(PMe3)Fe(\u03b72-H2)H.
\r\n\r\nAn equilibrium method for the determination of relative Ru-X and Ru-Y bond strengths in Cp*(PMe3)2RuX has been developed. A linear correlation of Ru-X to H-X bond strengths has been found over a wide range of ligands, X. The relationship is found to be general for a number of metal centers.
\r\n\r\nA study of the kinetics of phosphine exchange for Cp*(PMe3)2RuX has been undertaken. The rate of phosphine loss can be abstracted from a treatment of the kinetics of approach to equilibrium. Lone pairs on X are found to promote ligand dissociation. Dative bond dissociation enthalpies are obtained if small, and constant, barriers for ligand recombination are assumed. The functional group approximation used in solution thermochemical studies is found to break down when large changes are made in the steric constraint at the metal center.
", "date": "1987", "date_type": "degree", "id_number": "CaltechTHESIS:10232019-091323168", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:10232019-091323168", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Melissa Ray", "deposited_by": "Mel Ray", "deposited_on": "2019-10-23 16:36:03", "doi": "10.7907/exhb-6f18", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "chair" }, { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" }, { "email": "chans@its.caltech.edu", "id": "Chan-S-I", "name": { "family": "Chan", "given": "Sunney I." }, "role": "member" }, { "email": "jlbchamp@caltech.edu", "id": "Beauchamp-J-L", "name": { "family": "Beauchamp", "given": "Jesse L." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1987-05-13", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. 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Cp*(\u03b75-C5(CH3)4CH2CH2CH2)Hf(OOCMe3), has been synthesized. One example has been structurally characterized, Cp*2Hf(OOCMe3)CH2CH3 crystallizes in space group P21/c, with a = 19.890(7)\u00c5, b = 8.746(4)\u00c5, c = 17.532(6)\u00c5, \u03b2 = 124.987(24)\u00b0, V = 2498(2)\u00c53, Z = 4 and RF = 0.054 (2222 reflections, I > 0). Despite the coordinative unsaturation of the hafnium center, the terl-butylperoxide ligand is coordinated in a mono-dentate ligand. The mode of decomposition of these species is highly dependent on the substituent R. For R = H, CH2CH3, CH2CH2CH3, CH2CH2CH2CH3, CH2CHMe2 a clean first order conversion to Cp*2Hf(OCMe3)(OR) is observed (for R CH2CH3, \u0394H\u01c2 = 19.6 kcal\u2022mol-1, \u0394S\u01c2 = -13 e.u.). These results are discussed in terms of a two step mechanism involving \u03b72-coordination of the terl-butylperoxide ligand. Homolytic O-O bond cleavage is observed upon heating of Cp*2Hf(OOCMe3) R (R = C6H6, meta-C6H3(CH3)2). In the presence of excess 9,10-dihydroanthracene thermolysis of Cp*2Hf(OOCMe3)C6H6 cleanly affords Cp*2Hf(C6H6)OH and HOCMe3 (\u0394H\u01c2 = 22.6 kcal\u2022mol-1, \u0394S\u01c2 = -9 e.u.). The O-O bond strength in these complexes is thus estimated to be 22 kcal\u2022mol-1.
\r\n\r\nCp*2Ta(CH2)H, Cp*2Ta(CHC6H5)H, Cp*2Ta(C6H4)H, Cp*2Ta(CH2=CH2)H and Cp*2Ta(CH2=CHMe)H react, presumably through Cp*2Ta-R intermediates, with H2O to give Cp*2Ta(O)H and alkane. Cp*2Ta(O)H was structurally characterized: space group P21/n, a= 13.073(3)\u00c5, b = 19.337(4)\u00c5, c = 16.002(3)\u00c5, \u03b2 = 108.66(2)\u00b0, V = 3832(1)\u00c53, Z = 8 and RF = 0.0672 (6730 reflections). Reaction of terlbutylhydroperoxide with these same starting materials ultimately yields Cp*2Ta(O)R and HOCMe3. Cp*2Ta(CH2=CHR)OH species are proposed as intermediates in the olefin hydride reactions. Cp*2Ta(O2)R species can be generated from the reaction of the same starting materials and O2. Lewis acids have been shown to promote oxygen insertion in these complexes.
", "date": "1987", "date_type": "degree", "id_number": "CaltechTHESIS:02192014-152435840", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:02192014-152435840", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "DuPont" }, { "agency": "Shell" } ] }, "collection": "CaltechTHESIS", "reviewer": "Tony Diaz", "deposited_by": "Benjamin Perez", "deposited_on": "2014-02-20 16:44:22", "doi": "10.7907/PF6E-KV88", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "id": "Collins-T-J", "name": { "family": "Collins", "given": "Terrence J." }, "role": "chair" }, { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" }, { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "member" }, { "email": "dadougherty@caltech.edu", "id": "Dougherty-D-A", "name": { "family": "Dougherty", "given": "Dennis A." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1987-06-08", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1987", "author_list": "Asselt, Allan van", "advisor_list": "Bercaw, John E.", "comittee_list": "Collins, Terrence J.; Bercaw, John E.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/11866", "eprint_id": 11866, "rev_number": 16, "documents": [ { "id": "/id/document/103892", "doc_id": 103892, "rev_number": 3, "files": [ { "id": "/id/file/309832", "fileid": 309832, "datasetid": "document", "objectid": 103892, "filename": "Thompson_ME_1986.pdf", "mime_type": "application/pdf", "hash": "d3e629e3ef1b588b29360a24603bab3e", "hash_type": "MD5", "filesize": 48913555, "mtime": "2019-10-28 19:18:44", "url": "/11866/1/Thompson_ME_1986.pdf" } ], "eprint_id": 11866, "pos": 1, "placement": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": 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"http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/103892" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/103892" } ] } } ], "eprint_status": "archive", "userid": 8820, "dir": "disk0/00/01/18/66", "datestamp": "2019-10-28 19:21:37", "lastmod": "2021-04-16 23:21:55", "status_changed": "2019-10-28 19:21:37", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Thompson-Mark-Edward", "name": { "family": "Thompson", "given": "Mark Edward" }, "show_email": "NO" } ] }, "title": "Synthesis and Investigations into the Reactivity of Electron Deficient Organoscandium Complexes", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "A new class of coordinatively unsaturated, monomeric scandium complexes, (Cp*2ScR (Cp* = \u03b75-C5(CH3)5; R = H, alkyl, aryl, halide) have been prepared. Cp*2ScCl is prepared by the reaction of ScCl3(THF)3 with LiCp*, and Cp*2ScR (R = CH3, C6H5, C6H4CH3, CH2C6H5) by the reaction of Cp*2ScCl with the appropriate organoalkali reagent. Cp*2ScR complexes react readily with H2 to give RH and Cp*2ScH. The hydride ligand exchanges rapidly with hydrogen gas and inserts olefins to give alkyl complexes (e.g. Cp*2ScCH2CH3). Cp*2ScH reacts with allene to give Cp*2Sc(\u03b73-CH2CH=CH2). Cp*2ScR and Cp*2ScH react with pyridine to give Cp*2Sc(C,N-\u03b72-C5H4N). The crystal structure of this complex was determined and is reported herein.
\r\n\r\nSpectroscopic data for Cp*2ScCH3 and Cp*2ScCH2CH3 and crystallographic data for the former indicate that the methyl ligand is bound to scandium in a conventional manner, while the ethyl ligand may participate in an agostic interaction.
\r\n\r\nThe reactions of scandium alkyl, aryl and hydride complexes were investigated. H/D exchange between H2, arenes and the 1\u00b0 and 2\u00b0 C-H bonds of alkanes is catalyzed by Cp*2ScH. In C6H6 solution Cp*2ScH and Cp*2ScC6H5 are in equilibrium, \u0394H\u00b0 = 6.7 \u00b1 0.3 kcal/mole and \u0394S\u00b0 = 1.5 \u00b1 0.1 e.u.. Thus in this system a scandium-hydride bond is 1.5 \u00b1 0.4 kcal/mole stronger than a scandium-phenyl bond. Cp*2ScCH3 reacts with a wide range of hydrocarbons (RH) by C-H bond activation to give CH4 and Cp*2ScR (RH = 13CH4, arenes, styrenes, propyne). From the reactions of Cp*2ScCH3 with styrenes, the activation parameters (\u0394H\u2021 = 11.5-12.6 kcal/mole, \u0394S\u2021 = -34 to -38 e.u.) for these C-H activation reactions were determined. A deuterium isotope effect of 2.9 is observed for the intermolecular activation of C-H in the reaction of Cp*2ScCH3 with benzene. Very small differences in the rates of vinylic C-H bond activation for CH2=CHC6H4X-para (X = CF3, OCH3), and the aryl C-H bonds of C6H5X (X = CF3, H, CH3, N(CH3)2), as well as the positional nonselectivity for the activation of the meta and para C-H bonds of toluene indicate that the scandium center does not interact substantially with the \u03c0-system of these substrates in the transition states for these reactions. Thus for these sterically encumbered organoscandium compounds, sp2 C-H bond activation occurs without formation of a \u03c0-complex. A general mechanism for these C-H and H-H activation reactions is proposed, and is termed \"\u03c3-bond metathesis\".
\r\n\r\nThe reactions of Cp*2ScR complexes {R = hydride, alkyl, aryl) with small olefins and alkynes were examined. The hydride, methyl and benzyl complexes function as ethylene polymerization catalysts, while Cp*2ScC6H5 does not react. Cp*2ScH and Cp*2ScCH3 react stoichiometrically with propene by a series of insertion and vinylic C-H activation reaction. The final scandium product in both cases is trans-Cp*2ScCH=CHCH3. The scandium allyl complex, Cp*2Sc(\u03b73-CH2CH=CH2), is not observed and is not a reaction intermediate.
", "date": "1986", "date_type": "degree", "id_number": "CaltechTHESIS:10252019-155031892", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:10252019-155031892", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Atlantic Richfield Foundation" } ] }, "collection": "CaltechTHESIS", "reviewer": "Melissa Ray", "deposited_by": "Mel Ray", "deposited_on": "2019-10-28 19:21:37", "doi": "10.7907/wcaf-jd79", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "id": "Collins-T-J", "name": { "family": "Collins", "given": "Terrence J." }, "role": "chair" }, { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" }, { "email": "rhg@caltech.edu", "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "role": "member" }, { "email": "chans@its.caltech.edu", "id": "Chan-S-I", "name": { "family": "Chan", "given": "Sunney I." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1985-08-19", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1986", "author_list": "Thompson, Mark Edward", "advisor_list": "Bercaw, John E.", "comittee_list": "Collins, Terrence J.; Bercaw, John E.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/8091", "eprint_id": 8091, "rev_number": 34, "documents": [ { "id": "/id/document/46233", "doc_id": 46233, "rev_number": 2, "files": [ { "id": "/id/file/135420", "fileid": 135420, "datasetid": "document", "objectid": 46233, "filename": "McDade 1985.pdf", "mime_type": "application/pdf", "hash": "77005334a871b7c6593f4af9adec1048", "hash_type": "MD5", "filesize": 24308452, "mtime": "2014-02-20 22:02:19", "url": "/8091/1/McDade 1985.pdf" } ], "eprint_id": 8091, "pos": 1, "placement": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": 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"http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/46240" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/46240" } ] } } ], "eprint_status": "archive", "userid": 50, "dir": "disk0/00/00/80/91", "datestamp": "2014-02-20 22:27:15", "lastmod": "2022-11-09 19:20:06", "status_changed": "2014-02-20 22:27:15", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "cmcdade29@verizon.net", "id": "McDade-Christine", "name": { "family": "McDade", "given": "Christine" }, "show_email": "YES" } ] }, "title": "Synthetic, Kinetic and Mechanistic Studies in Early Transition Metal Systems. I. \u03b1- and \u03b2-Hydrogen Elimination Reactions in Derivatives of Permethyltitanocene, -Zirconocene, and -Hafnocene. II. The Reactions of Aluminum Alkyls with Derivatives of Permethylniobocene", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "note": "Thesis title listed in 1985 Commencement Program varies from actual thesis: Synthetic, Kinetic and Mechanistic Studies in Early Transition Metal Systems. I. \u03b1- and \u03b2-Hydrogen Elimination in Derivatives of Permethyltitanocene, -Zirconocene, and -Hafnocene. II. The reactions of Aluminum Alkyls with Derivatives of Permethylniobocene.", "abstract": "The thermal decomposition of Cp*2Ti(CH3)2 (Cp* \u2261 \u019e5-C5Me5) toluene solution follows cleanly first-order kinetics and produces a single titanium product Cp*(C5Me4CH2)Ti(CH3) concurrent with the evolution of one equivalent of methane. Labeling studies using Cp*2Ti-(CD3)2 and (Cp*-d15)2Ti(CH3)2 show the decomposition to be intramolecular and the methane to be produced by the coupling of a methyl group with a hydrogen from the other TiCH3 group. Activation parameters, \u0394H\u2021 and \u0394S\u2021, and kinetic deuterium isotope effects have been measured. The alternative decomposition pathways of \u03b1-hydrogen abstraction and a-hydrogen elimination, both leading to a titanium-methylidene intermediate, are discussed.
\r\n\r\nThe insertion of unactivated acetylenes into the metal-hydride bonds of Cp*2MH2 (M = Zr, Hf) proceeds rapidly at low temperature to form mono- and/or bisinsertion products, dependent upon the steric bulk of the acetylene substituents. Cp*2M(H)(C(Me) = CHMe), Cp*2M(H)(CH = CHCMe3), Cp*2M(H)-(CH = CHPh), Cp*2M(CH = CHPh)2, Cp*2M(CH = CHCH3)2 and Cp*2Zr-(CH = CHCH2CH3)2 have been isolated and characterized. To extend the study of unsaturated-carbon ligands, Cp*2M(C \u2261 CCH3)2 have been prepared by treating Cp*2MCl2 with LiC \u2261 CCH3. The reactivity of many of these complexes with carbon monoxide and dihydrogen is surveyed. The mono(2-butenyl) complexes Cp*2M(H)(C(Me) = CHMe) rearrange at room temperature, forming the crotyl-hydride species Cp*2M(H)(\u019e3-C4H7). The bis(propenyl) and bis(l-butenyl) zirconium complexes Cp*2Zr(CH = CHR)2 (R = CH3, CH2CH3) also rearrange, forming zirconacyclopentenes. Labeling studies, reaction chemistry, and kinetic measurements, including deuterium isotope effects, demonstrate that the unusual \u03b2-hydrogen elimination from an sp2-hybridized carbon is the first step in these latter rearrangements but is not observed in the former. Details of these mechanisms and the differences in reactivity of the zirconium and hafnium complexes are discussed.
\r\n\r\nThe reactions of hydride- and alkyl-carbonyl derivatives of permethylniobocene with equimolar amounts of trialkylaluminum reagents occur rapidly producing the carbonyl adducts Cp*2Nb(R)(COAlR'3) (R = H, CH3, CH2CH3, CH2CH2Ph, C(Me) = CHMe; R' = Me, Et). The hydride adduct Cp*2NbH3\u2022AlEt3 has also been formed. In solution, each of these compounds exists in equilibrium with the uncomplexed species. The formation constants for Cp*2Nb(H)(COAlR'3) have been measured. They indicate the steric bulk of the Cp* ligands plays a deciding factor in the isolation of the first example of an aluminum Lewis acid bound to a carbonyl-oxygen in preference to a metalhydride. Reactions of Cp*2Nb(H)CO with other Lewis acids and of the one:one adducts with H2, CO and C2H4 are also discussed.
\r\n\r\nCp*2Nb(H)(C2H4) also reacts with equimolar amounts of trialkyl-aluminum reagents, forming a one:one complex that 1H NMR spectroscopy indicates contains a Nb-CH2CH2-Al bridge. This adduct also exists in equilibrium with the uncomplexed species in solution. The formation constant for Cp*2Nb+(H)(CH2CH2Al-Et3) has been measured. Reactions of Cp*2Nb(H)(C2H4) with other Lewis acids and the reactions of Cp*2Nb+(H-(CH2CH2Al-Et3) with CO and C2H4 are described, as are the reactions of Cp*2Nb(H)(CH2 = CHR) (R = Me, Ph), Cp*2Nb(H)(CH3C \u2261 CCH3) and Cp*2Ti-(C2H4) with AlEt3.
", "date": "1985", "date_type": "degree", "id_number": "CaltechTHESIS:02202014-135322611", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:02202014-135322611", "related_url": { "items": [ { "description": "Article adapted for Chapter I.", "type": "doi", "url": "https://doi.org/10.1021/om00072a015" }, { "description": "Article adapted for Chapter II.", "type": "doi", "url": "https://doi.org/10.1016/0022-328x(85)87025-x" } ] }, "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" }, { "agency": "Tyler Foundation" } ] }, "collection": "CaltechTHESIS", "reviewer": "Tony Diaz", "deposited_on": "2014-02-20 22:27:15", "doi": "10.7907/B308-3A48", "alt_title": { "items": [ "Synthetic, Kinetic and Mechanistic Studies in Early Transition Metal Systems. I. \u03b1- and \u03b2-Hydrogen Elimination in Derivatives of Permethyltitanocene, -Zirconocene, and -Hafnocene. II. The reactions of Aluminum Alkyls with Derivatives of Permethylniobocene", "\u03b1- and \u03b2-Hydrogen Elimination Reactions in Derivatives of Permethyltitanocene, -Zirconocene, and -Hafnocene", "\u03b1- and \u03b2-Hydrogen Elimination in Derivatives of Permethyltitanocene, -Zirconocene, and -Hafnocene", "The Reactions of Aluminum Alkyls with Derivatives of Permethylniobocene" ] }, "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "id": "Collins-T-J", "name": { "family": "Collins", "given": "Terrence J." }, "role": "chair" }, { "email": "dadougherty@caltech.edu", "id": "Dougherty-D-A", "name": { "family": "Dougherty", "given": "Dennis A." }, "role": "member" }, { "email": "rhg@caltech.edu", "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "role": "member" }, { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1984-10-23", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1985", "author_list": "McDade, Christine", "advisor_list": "Bercaw, John E.", "comittee_list": "Collins, Terrence J.; Dougherty, Dennis A.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/11346", "eprint_id": 11346, "rev_number": 20, "documents": [ { "id": "/id/document/96259", "doc_id": 96259, "rev_number": 4, "files": [ { "id": "/id/file/275399", "fileid": 275399, "datasetid": "document", "objectid": 96259, "filename": "Spies_GH_1985.pdf", "mime_type": "application/pdf", "hash": "7be4fb8ace991afef5dba978f799f507", "hash_type": "MD5", "filesize": 81270769, "mtime": "2019-01-18 19:02:22", "url": "/11346/1/Spies_GH_1985.pdf" } ], "eprint_id": 11346, "pos": 1, "placement": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", 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"/id/document/96259" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/96259" } ] } } ], "eprint_status": "archive", "userid": 11566, "dir": "disk0/00/01/13/46", "datestamp": "2019-01-18 20:11:58", "lastmod": "2021-04-19 22:33:09", "status_changed": "2019-01-18 20:11:58", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Spies-George-Harlan", "name": { "family": "Spies", "given": "George Harlan" }, "show_email": "NO" } ] }, "title": "I. Studies on the Coordination of Bis-hydroxybenzamido Chelating Ligations to Chromium, Iron, and Osmium. II. A Survey of the Organometallic Chemistry of Osmium Tetraoxide", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "The coordination chemistry of chromium, iron, and osmium with bis-hydroxybenzamido chelating ligands was investigated. Two types of complexes were obtained on reacting CrCl3 \u2022 6H2O with 1,2-bis(3,5-dichloro-2-hydroxybenzanido)-ethane ((H)4CHBA-Et). A neutral dimeric complex, in which two chelates bridge two metal centers, was discovered and characterized by X-ray crystallography. This is the first molecule in which both forms of monodentate organic amide coordination (i.e., O-bound and N-bound coordination) have been found. The N-bound amide was shown to be a better \u03c3-donor. This is the first well-characterized example of N-coordination to chromium(III).
\r\n\r\nA second complex, which is a precursor to the neutral dimer, has not been fully characterized. It may also be dimeric. Similar complexes, with different bis-hydroxybenzamido ligands, have been examined. Iron(III) species, synthesized from these ligands and FeCl3, appear to be analogous to the latter chromium(III) compounds.
\r\n\r\nX-ray crystallographic studies have complemented investigations into the coordination chemistry of these bis-hydroxybenzamido ligands with several transition metals. In addition to the dimeric chromium(III) complex, in which the ligand bridges two metal centers, many osmium(IV) complexes were found with the bis-hydroxybenzamido ligands coordinated to one metal center as a planar tetradentate tetraanion. These structures exhibited the first examples of bonds between osmium(IV) and an N-coordinated organic amide ligand and a phenoxide ligand. One such complex, a \u00b5-oxo dimer, was found with potassium ions in unusually low coordination environments (i.e., four- and five-coordinate). Oxidation of trans-Os( CHBA-Et)(py)2 subsequently resulted in crystals of a new con1plex with a hydroxy and a methoxy group on the ethylene unit bridging the amide nitrogen atoms of the chelated ligand. The bond distances and angles for this molecule are very similar to those of its precursor, trans-Os(CHBA-Et)(py)2. The ligand, (H)4 CHBA-Et, was found to cocrystallize with pyridinium chloride. This structure has provided a benchmark for comparison with complexed chelates; few significant differences were observed.
\r\n\r\nThe fusion of 2,3-bis(2-hydroxy-benzamido)-2,3-butane with (NH4)2OsCl6 (T > 300\u00b0C) resulted in the formation of an osmium(IV)-imidazoline complex.
\r\n\r\nAlso examined was the organometallic chemistry of osmium tetraoxide. Oxidation of low valent carbonyl complexes with the quinuclidine adduct of osmium tetraoxide resulted in attack of both the low valent metal and a carbonyl ligand with the formation of \u00b5-CO2 mixed-valent complexes. The surprising stability of this new type of CO2 complex is kinetic in origin as den1onstrated by the chemistry of a series of compounds. Decomposition with loss of CO2 was observed for more labile metal complexes. In the absence of nitrogenous bases, oxidation of Ru(CO)3(PPh3)2 with osmium tetraoxide resulted in the formation of what is believed to be a tetranuclear complex. The low valent metal center and a coordinated carbonyl ligand were oxidized.
\r\n\r\nOne other mode of reactivity was discovered. Oxidative addition of osmium tetraoxide to Pt(PPh3)2(C2H4) displaced the ethylene ligand with the formation of a \u00b5-oxo bridged tetranuclear complex. These and other potential modes of OsO4 reactivity with organometallic and inorganic complexes are discussed.
", "date": "1985", "date_type": "degree", "id_number": "CaltechTHESIS:01182019-103133548", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:01182019-103133548", "related_url": { "items": [ { "description": "Publications from Appendix D.", "type": "doi", "url": "https://doi.org/10.1021/ja00389a093" }, { "description": "Publications from Appendix D.", "type": "doi", "url": "https://doi.org/10.1039/c39830000681" }, { "description": "Publications from Appendix D.", "type": "doi", "url": "https://doi.org/10.1039/c39840000198" }, { "description": "Publications from Appendix D.", "type": "doi", "url": "https://doi.org/10.1021/ja00328a028" } ] }, "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Melissa Ray", "deposited_on": "2019-01-18 20:11:58", "doi": "10.7907/s19j-2033", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" }, { "id": "Collins-T-J", "name": { "family": "Collins", "given": "Terrence J." }, "role": "co-advisor" } ] }, "thesis_committee": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "chair" }, { "id": "Collins-T-J", "name": { "family": "Collins", "given": "Terrence J." }, "role": "member" }, { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "member" }, { "email": "wag@caltech.edu", "id": "Goddard-W-A-III", "name": { "family": "Goddard", "given": "William A., III" }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1984-10-04", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1985", "author_list": "Spies, George Harlan", "advisor_list": "Bercaw, John E. and Collins, Terrence J.", "comittee_list": "Bercaw, John E.; Collins, Terrence J.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/11365", "eprint_id": 11365, "rev_number": 22, "documents": [ { "id": "/id/document/96425", "doc_id": 96425, "rev_number": 4, "files": [ { "id": "/id/file/276287", "fileid": 276287, "datasetid": "document", "objectid": 96425, "filename": "Krafft_TE_1985.pdf", "mime_type": "application/pdf", "hash": "bdad4b913fd9498be67f88911ec506d2", "hash_type": "MD5", "filesize": 62023046, "mtime": "2019-01-30 18:18:05", "url": "/11365/1/Krafft_TE_1985.pdf" } ], "eprint_id": 11365, "pos": 1, "placement": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": 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"http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/96425" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/96425" } ] } } ], "eprint_status": "archive", "userid": 11566, "dir": "disk0/00/01/13/65", "datestamp": "2019-01-31 02:12:16", "lastmod": "2021-04-16 22:26:44", "status_changed": "2019-01-31 02:12:16", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Krafft-Terry-Edward", "name": { "family": "Krafft", "given": "Terry Edward" }, "show_email": "NO" } ] }, "title": "The Design Multianionic Chelating Ligands for the Production of Inorganic Oxidizing Agents, Synthesis, Structure and Reactivity of Osmium Complexes Derived from a Tetradentate Ligand", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "The design of multianionic chelating ligands for use in high valent transition metal chemistry is discussed. Possible application of such ligands to problems in inorganic oxidation chemistry is addressed. A class of potentially tetradentate tetraanionic ligands was synthesized. The ligand 1,2-bis(3,5-dichloro-2-hydroxybenzamido)ethane (H4CHBA-Et), 1, was found to coordinate to osmium as a tetradentate tetraanion in the oxidation states (II), (III), (IV), (V), and (VI). X-ray crystal structures of two osmium(IV) complexes of this ligand are reported. The \u00b5-oxo dimer, K2({Os(\u03b74-CHBA-Et)(OPPh3)}2-O], 3, features octahedral osmium with the tetradentate tetraanionic ligand 1 coordinated to the equatorial positions and the potassium ions in unusual coordination environments. The structure of octahedral Os(\u03b74-CHBAEt)(py)2,5, shows the ligand 1 coordinated in the same fashion with pyridines in the axial positions.
\r\n\r\nCompound 5 and all of the osmium(IV) compounds reported here exhibit well-resolved paramagnetically shifted NMR spectra. The 1H NMR data suggest the possibility of an unusual \u03c0-backbonding interaction from osmium(IV) to pyridine. Electrochemical data indicate that ligand 1 and related ligands have a profound effect on the osmium redox couples which are found at significantly lower potentials than with other ligands.
\r\n\r\nControlled potential oxidation of 5 in the presence of water or alcohol was found to trigger a series of irreversible chemical and electrochemical transformations in which the ethane backbone of the ligand is oxidized in a selective and stepwise fashion. Several key intermediates have been isolated, independently synthesized and characterized. The first intermediate isolated, Os(\u03b74-CHBA-ethylene)(py)2, 7, results from dehydrogenation of the ligand bridge. An X-ray crystal structure of this material is reported and significant features are discussed. In the second isolated intermediate the unsaturated ethylene bridge of 7 has been oxidized to a trans-1,2-diether in compound 8. A crystal structure of the related trans-1,2-hydroxy-alkoxy complex, 8*, has been performed. Cleavage of the bridge carbon-carbon bond in 8 yields the final oxidation products cis-\u03b1 and trans-Os(\u03b72-Fo-CHBA)2-(py)2, 9 and 9', in which the amide nitrogen of each bidentate ligand is substituted with a formyl group. t-Bupy derivatives of both isomers have been characterized by X-ray crystal structure determinations. The diastereomeric distribution is determined by the nature of the alcohol in solution during the electrolysis. Mechanistic aspects of the ligand oxidation process are addressed.
\r\n\r\nCompounds 9 and 9' can be converted to catalysts for the electrochemical oxidation of alcohols. The catalysts were found to be the osmium(IV) compounds cis-\u03b1- and trans-Os(\u03b72-CHBA)2(t-Bupy)2, 11 and 11', which are formed by a selective stepwise hydrolysis of the two formyl groups in 9/9'. A crystal structure of 11' shows the primary amide group of 3,5-dichloro-2-hydroxybenzamide, H2CHBA, to be coordinated through nitrogen. Chemical synthesis of the catalysts was pursued by coordination of H2CHBA to osmium. Two of the ligands coordinate to osmium(VI) as bidentate dianions in the complex K2 (Os(\u03b72-CHBA)2(O)2), 12, which can be converted to 11', 15 and the compounds trans and cis-Os(\u03b72-CHBA)2(t-Bupy)(Ph3P=O), 13 and 14. Compound 15 has been formulated as the dimer Os2(\u03b72-CHBA)4(t-Bupy)4.
\r\n\r\nCompounds 11, 11', 13 and 14 are catalysts for the electrochemical oxidation of alcohols. The catalytic system selectively oxidizes benzyl alcohol to benzaldehyde without further oxidation to benzoic acid or benzyl esters. Approximately 150 molecules of benzyl alcohol are oxidized during the lifetime of the catalyst, 11, but activity with other alcohols is quite low. The synthesis, characterization and properties of the above osmium compounds and significant features of the catalytic system are reported.
\r\n\r\n", "date": "1985", "date_type": "degree", "id_number": "CaltechTHESIS:01302019-091842152", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:01302019-091842152", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Melissa Ray", "deposited_on": "2019-01-31 02:12:16", "doi": "10.7907/sts6-x769", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "chair" }, { "id": "Collins-T-J", "name": { "family": "Collins", "given": "Terrence J." }, "role": "member" }, { "email": "jlbchamp@caltech.edu", "id": "Beauchamp-J-L", "name": { "family": "Beauchamp", "given": "Jesse L." }, "role": "member" }, { "email": "rhg@caltech.edu", "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1985-02-07", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1985", "author_list": "Krafft, Terry Edward", "advisor_list": "Bercaw, John E.", "comittee_list": "Bercaw, John E.; Collins, Terrence J.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/11319", "eprint_id": 11319, "rev_number": 23, "documents": [ { "id": "/id/document/95711", "doc_id": 95711, "rev_number": 4, "files": [ { "id": "/id/file/273587", "fileid": 273587, "datasetid": "document", "objectid": 95711, "filename": "Coolbaugh_TS_1985.pdf", "mime_type": "application/pdf", "hash": "7d967fef5238eb40f4c15e9d28711355", "hash_type": "MD5", "filesize": 46132368, "mtime": "2018-12-17 20:57:05", "url": "/11319/1/Coolbaugh_TS_1985.pdf" } ], "eprint_id": 11319, "pos": 1, "placement": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": 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"http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/95711" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/95711" } ] } } ], "eprint_status": "archive", "userid": 11566, "dir": "disk0/00/01/13/19", "datestamp": "2018-12-19 17:46:59", "lastmod": "2021-04-16 23:21:20", "status_changed": "2018-12-19 17:46:59", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Coolbaugh-Thomas-Smith", "name": { "family": "Coolbaugh", "given": "Thomas Smith" }, "show_email": "NO" } ] }, "title": "Nucleophilic Activation of Carbon Monoxide: Synthesis, Characterization and Reactivity of Intramolecular Group VI Metallaesters", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "An investigation of the design and reactivity of bifunctional transition metal complexes pertinent to homogeneous reduction of carbon monoxide is presented. Oxygen nucleophiles were incorporated into Group VI metal carbonyl complexes via cyclopentadienyl ligands.
\r\n\r\nNeutral molybdenum dimers yield no intramolecular nucleophilic interaction between an alcohol, attached by different bridging arm lengths, and the metal carbonyl fragment. A crystal structure of the propanol substituted cyclopentadienyl molybdenum tricarbonyl dimer (space group P1, a = 7.487 \u00c5,\r\nb = 7.713 \u00c5, c = 10.902 \u00c5, \u03b1 = 99.3600\u00b0, \u03b2 = 81.460\u00b0, \u03b3 = 115.260\u00b0, V = 563.0 \u00c53, Z = 1) indicates only an intermolecular hydrogen bond between alcohols.
\r\n\r\nThe synthesis of the cationic compounds, [CpRM(CO)3L]+BF-4 is reported, where M = Mo, W and R = -(CH2)\u03b7 - OH with n = 1-3. Deprotonation of the alcohols leads to intramolecular metallaester formation for the methylene and ethylene bridged compounds. The equilibria established upon reaction with external alcohols are reported as are the thermodynamic parameters associated with the process.
\r\n\r\nCrystal structures of the metallaesters bridged by a methylene (space group P21/n, a = 7.867 \u00c5, b = 17.083 \u00c5, c = 17.768 \u00c5, \u03b2= 100.959\u00b0, V = 2344.4 \u00c53, Z = 4) and ethylene group (space group P21/n, a = 8.127 \u00c5, b = 16.823 \u00c5, c = 17.623 \u00c5, \u03b2 = 101.980\u00b0, V = 2357.1 \u00c53, Z = 4) are presented. A comparison of the structures is given.
\r\n\r\nReaction of the intramolecular metallaesters with molecular hydrogen produces no volatile products. Reaction with stoichiometric hydride sources yields compounds of relevance to carbon monoxide reduction. Reactions with Me+ and water are presented, the latter giving rise to a stoichiometric analog of the water-gas shift reaction.
", "date": "1985", "date_type": "degree", "id_number": "CaltechTHESIS:12172018-123100783", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:12172018-123100783", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Tony Diaz", "deposited_on": "2018-12-19 17:46:59", "doi": "10.7907/aps3-bk95", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" }, { "email": "rhg@caltech.edu", "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "role": "co-advisor" } ] }, "thesis_committee": { "items": [ { "email": "rhg@caltech.edu", "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "role": "chair" }, { "id": "Schaefer-W-P", "name": { "family": "Schaefer", "given": "William P." }, "role": "member" }, { "email": "dadougherty@caltech.edu", "id": "Dougherty-D-A", "name": { "family": "Dougherty", "given": "Dennis A." }, "role": "member" }, { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1984-06-20", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1985", "author_list": "Coolbaugh, Thomas Smith", "advisor_list": "Bercaw, John E. and Grubbs, Robert H.", "comittee_list": "Grubbs, Robert H.; Schaefer, William P.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/11285", "eprint_id": 11285, "rev_number": 16, "documents": [ { "id": "/id/document/95285", "doc_id": 95285, "rev_number": 4, "files": [ { "id": "/id/file/271508", "fileid": 271508, "datasetid": "document", "objectid": 95285, "filename": "Lee_C-W_1984.pdf", "mime_type": "application/pdf", "hash": "105c65c872314ff3cc434771f2acbef2", "hash_type": "MD5", "filesize": 32975907, "mtime": "2018-11-27 17:28:39", "url": "/11285/1/Lee_C-W_1984.pdf" } ], "eprint_id": 11285, "pos": 1, "placement": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": 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"http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/95285" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/95285" } ] } } ], "eprint_status": "archive", "userid": 11566, "dir": "disk0/00/01/12/85", "datestamp": "2018-11-27 21:15:15", "lastmod": "2021-04-16 23:25:45", "status_changed": "2018-11-27 21:15:15", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Lee-Chi-Woo", "name": { "family": "Lee", "given": "Chi-Woo" }, "show_email": "NO" } ] }, "title": "Adsorption and Electrochemistry of BIS-1, 10-Phenanthroline Complexes of Copper (I,II) and Fungal Laccase A", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "This thesis is an outcome of the efforts directed toward the theme \"Electrocatalysis of dioxygen reduction by copper- containing molecules adsorbed on graphite electrodes.\"
\r\n\r\nIn the first part, an electrochemical measurement of the rate of electron exchange between Cu(phen)2+ adsorbed on graphite and Cu(phen)2++ in solution is described. The rate constant was estimated to be ca. 105 M-1 s-1 by using rotating disk voltammetry. The origin of the previously reported but widely discrepant values (5 x 107 M-1 s-1 and 50 M-1 s-1) in the literature is discussed, and a new estimate of ca. 104 M-1 s-1 is obtained by applying Marcus theory in a form that allows explicitly for differences in reorganization energy between the oxidized and reduced halves of the reacting redox couples. The electrocatalytic studies of dioxygen reduction by Cu(phen)2+ could not be done due to the low signal-to-noise ratio.
\r\n\r\nIn the second part, the bioelectrocatalytic reduction of molecular oxygen by reduced fungal laccase A immobilized on pyrolytic graphite is described. The reduction produces exclusively water in the potential range studied (< 0 V vs. SSCE). The catalytic activity reaches its maximum at pH 3~4, and the lower limit on rate constant for the reduction in this pH range was estimated to be 1.5 x 104 M-1 s-1.
\r\n\r\nThree appendices describe (i) potential step hydrodynamic chronocoulometry, (ii) a new method to determine the self- exchange rate constant for the redox couple in which the coordination numbers depend on the oxidation states, and (iii) a novel electrochemical method of detecting H2O2.
\r\n", "date": "1984", "date_type": "degree", "id_number": "CaltechTHESIS:11272018-091510836", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:11272018-091510836", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "deposited_on": "2018-11-27 21:15:15", "doi": "10.7907/f4sv-x904", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." }, "role": "chair" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "member" }, { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "Rudolph A." }, "role": "member" }, { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1983-10-10", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1984", "author_list": "Lee, Chi-Woo", "advisor_list": "Bercaw, John E.", "comittee_list": "Anson, Fred C.; Gray, Harry B.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/11882", "eprint_id": 11882, "rev_number": 22, "documents": [ { "id": "/id/document/140521", "doc_id": 140521, "rev_number": 2, "files": [ { "id": "/id/file/419866", "fileid": 419866, "datasetid": "document", "objectid": 140521, "filename": "Ott_KC_1982.pdf", "mime_type": "application/pdf", "hash": "4a06bf798dc9d09b6cdd864bade9b935", "hash_type": "MD5", "filesize": 52440542, "mtime": "2023-10-31 22:46:16", "url": "/11882/6/Ott_KC_1982.pdf" } ], "eprint_id": 11882, "pos": 6, "placement": 6, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": "Ott_KC_1982.pdf", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "final" }, { "id": "/id/document/140522", "doc_id": 140522, "rev_number": 3, "files": [ { "id": "/id/file/419870", "fileid": 419870, "datasetid": "document", "objectid": 140522, "filename": "Ott_KC_1982.zip", "mime_type": "application/zip", "hash": "ab25b256a4e2a993804c3239c86a2fbf", "hash_type": "MD5", "filesize": 129007903, "mtime": "2023-10-31 22:46:37", "url": "/11882/7/Ott_KC_1982.zip" } ], "eprint_id": 11882, "pos": 7, "placement": 7, "mime_type": "application/zip", "format": "application/zip", "format_desc": "TIFF files", "language": "en", "security": "internal", "license": "other", "main": "Ott_KC_1982.zip", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "archival" }, { "id": "/id/document/140524", "doc_id": 140524, "rev_number": 1, "files": [ { "id": "/id/file/419875", "fileid": 419875, "datasetid": "document", "objectid": 140524, "filename": "indexcodes.txt", "mime_type": "text/plain", "hash": "d34907fb069c26aeb0842f125e79a071", "hash_type": "MD5", "filesize": 22077, "mtime": "2023-10-31 22:56:46", "url": "/11882/8/indexcodes.txt" } ], "eprint_id": 11882, "pos": 8, "placement": 8, "mime_type": "text/plain", "format": "other", "format_desc": "Generate index codes conversion from application/pdf to indexcodes", "language": "en", "security": "public", "license": "other", "main": "indexcodes.txt", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/140521" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/140521" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/140521" } ] } } ], "eprint_status": "archive", "userid": 8820, "dir": "disk0/00/01/18/82", "datestamp": "2019-11-01 23:45:00", "lastmod": "2023-10-31 22:47:20", "status_changed": "2019-11-01 23:45:00", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Ott-Kevin-Curtis", "name": { "family": "Ott", "given": "Kevin Curtis" }, "show_email": "NO" } ] }, "title": "Some Mechanistic and Synthetic Aspects of the Interaction of Lewis Acids with Bis-Cyclopentadienyltitanium(IV) Alkyls and Bis-Cyclopentadienyltitanacyclobutanes", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "Titanocene dichloride has been shown to react cleanly with two equivalents of AlMe3 to produce the Lewis acid stabilized titanium methylene [chemical formula; see abstract in scanned thesis for details]. Due to the interest in the utility of this complex in Wittig-type chemistry, in the metathesis of olefins, and in the synthesis of titanacyclobutanes, a study of the mechanism of formation of the complex was carried out. The proposed mechanism for formation of 1 involves an intramolecular proton abstraction by an Al-Me bond from a Ti-CH3 group in the intermediate Cp2TiMeCl\u2022AlMe3. The effect of Cp-ring substitution and halide substitution on the reaction rate along with a deuterium isotope effect of 3 and a large negative entropy of activation were consonant with the proposed mechanism.
\r\n\r\nSpecifically labelled titanacyclobutanes were prepared, and the cleavage reaction with AlMe2Cl to yield 1 as studied. It was found that cleavage occurred with a secondary deuterium isotope of 1.2 to 1.6 (depending upon the titanacyclobutane) and exhibited bimolecular kinetics. Surprisingly, the stereochemistry of the titanacyclobutanes was completely scrambled before cleavage to 1 and olefin. A mechanism for this isomerization was proposed to involve a rapid and reversible trans-metallation of a Ti-C bond with AlMe2Cl, producing a 3-aluminapropyltitanocene chloride. Following rapid inversion at the carbon adjacent to aluminum, the racemized 3-aluminapropyltitanocene chloride could cleave to 1 or close to yield isomerized titanacyclobutane.
\r\n\r\nThe \u03b2,\u03b2-disubstituted titanacyclobutanes proved to be good sources of the Cp2TiCH2 unit, as indicated by their ready formation of bis-\u00b5-CH2-bis-Cp2Ti (2). Some chemistry and photochemistry of 2 are reported. The Cp2TiCH2 moiety is readily trapped with transiton metal or main group metal Lewis acids such as Cp^TiCl3 or Me3SnCl to produce compounds such as [Cp2TiCl]-\u00b5-CH2-[Cp*TiCl2] (3) and Cp2Ti(CH2SnMe3)Cl. Cp2TiCH2 may also be trapped as the methylene phosphine adduct Cp2Ti(=CH2)PEt3 (4).
\r\n\r\nThe compounds 2 and 3 react with CO to yield insertion products which contain bridging ketene ligands which w ere characterized spectroscopically. Compound 4 also reacts with CO to produce the mononuclear ketene Cp2Ti(\u03b72-CH2CO) in low yield.
", "date": "1983", "date_type": "degree", "id_number": "CaltechTHESIS:11012019-155844929", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:11012019-155844929", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Melissa Ray", "deposited_by": "Mel Ray", "deposited_on": "2019-11-01 23:45:00", "doi": "10.7907/fxvt-ac87", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "rhg@caltech.edu", "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "role": "chair" }, { "email": "dadougherty@caltech.edu", "id": "Dougherty-D-A", "name": { "family": "Dougherty", "given": "Dennis A." }, "role": "member" }, { "id": "Evans-David-A", "name": { "family": "Evans", "given": "David A." }, "role": "member" }, { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1982-06-03", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1983", "author_list": "Ott, Kevin Curtis", "advisor_list": "Bercaw, John E.", "comittee_list": "Grubbs, Robert H.; Dougherty, Dennis A.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/5757", "eprint_id": 5757, "rev_number": 15, "documents": [ { "id": "/id/document/9933", "doc_id": 9933, "rev_number": 5, "files": [ { "id": "/id/file/64251", "fileid": 64251, "datasetid": "document", "objectid": 9933, "filename": "Olsen_w_1983.pdf", "mime_type": "application/pdf", "filesize": 3021555, "mtime": "2012-12-26 03:25:01", "url": "/5757/1/Olsen_w_1983.pdf" } ], "eprint_id": 5757, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": "Olsen_w_1983.pdf", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "final", "relation": { "items": [ { "type": "http://eprints.org/relation/hasVolatileVersion", "uri": "/id/document/25796" }, { "type": "http://eprints.org/relation/haspreviewThumbnailVersion", "uri": "/id/document/25796" }, { "type": "http://eprints.org/relation/hasVersion", "uri": "/id/document/25796" } ] } }, { "id": "/id/document/10710", "doc_id": 10710, "rev_number": 3, "files": [ { "id": "/id/file/205394", "fileid": 205394, "datasetid": "document", "objectid": 10710, "filename": "Olsen_w_1983.zip", "mime_type": "application/zip", "filesize": 5874276, "mtime": "2016-08-22 21:19:11", "url": "/5757/2/Olsen_w_1983.zip" } ], "eprint_id": 5757, "pos": 2, "format": "application/zip", "format_desc": "TIFF", "language": "en", "security": "internal", "license": "other", "main": "Olsen_w_1983.zip", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "final" }, { "id": "/id/document/25796", "doc_id": 25796, "rev_number": 3, "files": [ { "id": "/id/file/64249", "fileid": 64249, "datasetid": "document", "objectid": 25796, "filename": "preview.png", "mime_type": "image/png", "hash": "40571012ecdf2b65798ef33ae22f196c", "hash_type": "MD5", "filesize": 8272, "mtime": "2012-12-26 03:25:01", "url": "/5757/3/preview.png" } ], "eprint_id": 5757, "pos": 3, "placement": 3, "mime_type": "image/png", "format": "image/png", "language": "en", "security": "public", "license": "other", "main": "preview.png", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/9933" }, { "type": "http://eprints.org/relation/ispreviewThumbnailVersionOf", "uri": "/id/document/9933" }, { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/9933" } ] } } ], "eprint_status": "archive", "userid": 51, "dir": "disk0/00/00/57/57", "datestamp": "2010-07-08 16:40:56", "lastmod": "2021-04-16 23:00:25", "status_changed": "2010-07-08 16:40:56", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Olson-W-A", "name": { "family": "Olson", "given": "Wendy A." }, "show_email": "NO" } ] }, "title": "The synthesis and reactivity of new niobium (V) polyhydrides", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "The synthesis of new niobium polyhydrides by high pressure hydrogenation of Cp*NbMe_4 in the presence of trapping phosphines is reported. The complexes Cp*NbL_2H_4, L=PMe_3, PMe_2Ph, PMe_2Cy, and L_2=bis(dimethylphosphino)ethane, are described. They exchange D_2 into the hydride positions, and react hydridically with methanol and acetone to give alkoxide species. Reactions with CO give reduced metal carbonyl phosphine complexes. All these reactions (except the reaction with methanol) appear to proceed with loss of phosphine as the rate limiting step. Reactions of the hydride species with group VI carbonyls, and with ethylene, are presented. The novel reactivity of Cp*Nb(PMe_2Ph)_2H_4 with H_2 to give Cp*Nb(PMe_2Cy)_2H_4 is discussed.", "date": "1983", "date_type": "degree", "id_number": "CaltechTHESIS:04292010-145411166", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:04292010-145411166", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "John Wade", "deposited_by": "Tony Diaz", "deposited_on": "2010-07-08 16:40:56", "doi": "10.7907/e6p9-e788", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "masters", "thesis_advisor": { "items": [ { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "name": { "family": "Unknown", "given": "Unknown" } } ] }, "thesis_degree": "MS", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1982-08-10", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1983", "author_list": "Olson, Wendy A.", "advisor_list": "Bercaw, John E.", "comittee_list": "Unknown, Unknown" }, { "id": "https://thesis.library.caltech.edu/id/eprint/11887", "eprint_id": 11887, "rev_number": 16, "documents": [ { "id": "/id/document/104114", "doc_id": 104114, "rev_number": 3, "files": [ { "id": "/id/file/310793", "fileid": 310793, "datasetid": "document", "objectid": 104114, "filename": "willett-bc-1983.pdf", "mime_type": "application/pdf", "hash": "f82b268331360c896fa9844b3d43419e", "hash_type": "MD5", "filesize": 9129463, "mtime": "2019-11-04 22:24:25", "url": "/11887/1/willett-bc-1983.pdf" } ], "eprint_id": 11887, "pos": 1, "placement": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": "willett-bc-1983.pdf", 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"0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/104114" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/104114" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/104114" } ] } } ], "eprint_status": "archive", "userid": 8820, "dir": "disk0/00/01/18/87", "datestamp": "2019-11-04 22:26:16", "lastmod": "2021-04-16 23:05:59", "status_changed": "2019-11-04 22:26:16", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Willett-Brian-Christopher", "name": { "family": "Willett", "given": "Brian Christopher" }, "show_email": "NO" } ] }, "title": "Electron Transfer Rates and Adsorption in the Electrochemistry of Cobalt-2,2'-Bipyridine, Ruthenium Ammine Thiocyanate Complexes and cis-[(C\u2085H\u2085)Fe(CO)P(C\u2086H\u2085)\u2082]\u2082", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "In Part I of this thesis, the electrochemical properties of cobalt(I)-2,2'-bipyridine and cobalt(I)-6,6'-dimethyl-2,2'-bipyridine complexes were investigated, including their reactions with reducible substrates and their adsorption on mercury electrodes.
\r\n\r\nElectron transfer rate constants measured for cyclooctatetraene and cis-[(C5H5)Fe(CO)P(C6H5)2]2, molecules which undergo large intramolecular rearrangements upon electron transfer, in non-aqueous solvents with various tetraalkylammonium salts as supporting electrolytes are presented in Part II. The electrode kinetics were measured by cyclic voltammetry, chronocoulometry and AC impedance techniques. Values of the rate constants found were as large as 0.30 cm/sec.
\r\n\r\nSynthesis and adsorption behavior of several novel substituted ruthenium ammine complexes are discussed in Part III. The adsorption on mercury was used to distinguish between the two thiocyanate linkage isomers, Ru(NH3)5NCS2+ and Ru(NH3)5SCN2+. The coordination properties of ruthenium(II) were used to prepare trans-Ru(NH3)4(NCS))4-vinyl- pyridine)Ru(EDTA), a binuclear ruthenium species.
", "date": "1983", "date_type": "degree", "id_number": "CaltechTHESIS:11042019-130341164", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:11042019-130341164", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Melissa Ray", "other_numbering_system": { "items": [ { "id": "8302622", "name": "UMI" } ] }, "suggestions": "Downloaded from UMI", "deposited_by": "Mel Ray", "deposited_on": "2019-11-04 22:26:16", "doi": "10.7907/t7fp-5z02", "alt_title": { "items": [ "Electron Transfer Rates and Adsorption in the Electrochemistry of Cobalt-2,2'-Bipyridine, Ruthenium Ammine Thiocyanate Complexes and cis-[(C5H5)Fe(CO)P(C6H5)2]2", "Electron Transfer Rates and Adsorption in the Electrochemistry of Cobalt-2,2'-Bipyridine, Ruthenium Ammine Thiocyanate Complexes and cis-[(C_(5)H_(5))Fe(CO)P(C_(6)H_(5))_(2)]_(2)" ] }, "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "chair" }, { "email": "fanson@caltech.edu", "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." }, "role": "member" }, { "email": "rhg@caltech.edu", "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "role": "member" }, { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1982-09-17", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1983", "author_list": "Willett, Brian Christopher", "advisor_list": "Bercaw, John E.", "comittee_list": "Bercaw, John E.; Anson, Fred C.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/8075", "eprint_id": 8075, "rev_number": 49, "documents": [ { "id": "/id/document/46056", "doc_id": 46056, "rev_number": 2, "files": [ { "id": "/id/file/134907", "fileid": 134907, "datasetid": "document", "objectid": 46056, "filename": "Cohen_sa_1982.pdf", "mime_type": "application/pdf", "hash": "dd8012d6105f4ae9eb083adb50dee4c2", "hash_type": "MD5", "filesize": 32151378, "mtime": "2014-02-13 19:55:16", "url": "/8075/1/Cohen_sa_1982.pdf" } ], "eprint_id": 8075, "pos": 1, "placement": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": 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I. Structure and Reactivity of a Titanium Ethylene Complex. II. Reactivity of Decamethyl Niobocene Derivatives", "ispublished": "unpub", "full_text_status": "public", "keywords": "Titanium, ethylene, niobium, metallacycle, organometallic", "abstract": "The synthesis and X-ray diffraction study of bis(pentamethylcyclopentadienyl) ethylene titanium (I) are reported. This complex represents the first example of an isolable ethylene adduct of a group IV metal, a key intermediate in Ziegler-Natta olefin polymerization schemes. While treatment of I with ethylene leads to only traces of polymer after months, I participates in a wide range of stoichiometric and catalytic reactions. These include the catalytic conversion of ethylene specifically to butadiene and ethane and the catalytic isomerization of alkenes. Detailed studies have been carried out on the stoichiometric reactions of I with nitriles and alkynes. At low temperatures, nitriles react to form metallacycloimine species which more slowly undergo a formal 1,3-hydrogen shift to generate metallacycloeneamines. The lowest energy pathway for this rearrangement is an intramolecular hydrogen shift which is sensitive to the steric bulk of the R substituent. The reactions of I with alkynes yield metallacyclopentene complexes with high regioisomer selectivity. Carbonylation of the metallacyclopentene (\u03b7-C5Me5)2TiC(CH3)=C(CH3)CH2CH2 under relatively mild conditions cleanly produces the corresponding cyclopentenone and [C5(CH3)5]2Ti(CO)2. Compounds derived from CO2 and acetaldehyde have also been isolated.
\r\n\r\nThe synthesis and characterization of bis-(\u03b7-pentamethylcyclopentadienyl) niobium(III) tetrahydroborate (II) are described and a study of its temperature-dependent proton NMR spectroscopic behavior is reported. The complex is observed to undergo a rapid intramolecular averaging process at elevated temperatures. The free energy of activation, \u0394G\u2260 = 16.4 \u00b1 0.4 kcal/mol, is calculated. The reinvestigation of a related compound, bis(\u03b7-cyclopentadienyl)niobium(III) tetrahydroborate, established \u0394G\u2260 = 14.6 \u00b1 0.2 kcal/mol for the hydrogen exchange process. The tetrahydroborate complex, II reacts with pyridine and dihydrogen to yield (\u03b7-C5Me5)2NbH3 (III). The reactivity of III with CO and ethylene is reported.
\r\n", "date": "1982", "date_type": "degree", "id_number": "CaltechTHESIS:02132014-115308678", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:02132014-115308678", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "deposited_by": "Benjamin Perez", "deposited_on": "2014-02-14 23:19:31", "doi": "10.7907/3DDT-0252", "alt_title": { "items": [ "I. Structure and Reactivity of a Titanium Ethylene Complex", "Structure and Reactivity of a Titanium Ethylene Complex", "II. Reactivity of Decamethyl Niobocene Derivatives", "Reactivity of Decamethyl Niobocene Derivatives" ] }, "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "chair" }, { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" }, { "id": "Marsh-R-E", "name": { "family": "Marsh", "given": "Richard Edward" }, "role": "member" }, { "email": "rhg@caltech.edu", "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1982-02-04", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1982", "author_list": "Cohen, Steven Alan", "advisor_list": "Bercaw, John E.", "comittee_list": "Gray, Harry B.; Bercaw, John E.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/4337", "eprint_id": 4337, "rev_number": 17, "documents": [ { "id": "/id/document/7095", "doc_id": 7095, "rev_number": 3, "files": [ { "id": "/id/file/43206", "fileid": 43206, "datasetid": "document", "objectid": 7095, "filename": "Biller_sa_1982.pdf", "mime_type": "application/pdf", "filesize": 18784687, "mtime": "2012-12-26 03:07:40", "url": "/4337/1/Biller_sa_1982.pdf" } ], "eprint_id": 4337, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "format_desc": "Original (no OCR) Biller_sa_1982.pdf", "language": "en", "security": "internal", "license": "other", "main": "Biller_sa_1982.pdf", 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(\u00b1)-naphthyridinomycin A is described. This research has thus far culminated in the preparation of the advanced, pentacyclic intermediate 93. The structure of phenol 93 was secured by an X-ray crystallographic study of its benzoate ester. Intermediate 93 was constructed from tricyclic lactam 21, phenol 19a and methyl glyoxalate, employing a stereoselective amidoalkylation reaction and an intramolecular Friedel-Crafts alkylation as key transformations. With regard to the amidoalkylation step, several new methods for the generation of acylimmonium ions were developed in the course of model studies. The synthesis of tricyclic lactam 21 from the readily available bicyclic \u03b2-lactam 31 was accomplished via a 13-step sequence, which included several interesting intramolecular reactions.
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I certify that the version I submitted is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive\nlicense to archive and make accessible, under the conditions specified below,\nmy thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation or project report. 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2, "dir": "disk0/00/00/09/05", "datestamp": "2005-03-09", "lastmod": "2020-06-18 19:24:54", "status_changed": "2009-09-25 01:50:04", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "maverick@lsu.edu", "id": "Maverick-Andrew-William", "name": { "family": "Maverick", "given": "Andrew William" }, "show_email": "YES" } ] }, "title": "Spectroscopy and Photochemistry of Polynuclear Metal Complexes", "ispublished": "unpub", "full_text_status": "public", "keywords": "Bromide; Chloride; Cluster; Isocyanide; Luminescence; Molybdenum; Photoredox; Rhodium; Tungsten", "abstract": "The photochemical and spectroscopic properties of two classes of polynuclear metal complexes have been studied.
\r\n\r\nMolybdenum and Tungsten Cluster Halides: The cubic ions Mo6Cl142-, Mo6Br142-, and W6Cl142- are luminescent, with lifetimes approaching 200 \u03bcs in solution at room temperature. The luminescent excited state of Mo6Cl142- is probably associated with a transition localized on the central Mo6 core. Both this excited state and the corresponding ground state undergo facile one electron oxidation. These features make the cluster ions attractive for experiments in photochemical energy storage. Also discussed is evidence from magnetic and spectroscopic studies bearing on the electronic structures of the cluster ions.
\r\n\r\nRhodium Isocyanide Complexes: Various thermal and photochemical reactions in the system Rh2b42+ - Rh4b86+ - Rh2b44+ (b = 1,3-diisocyanopropane) have been examined. The possibility of photocatalytic hydrogen production sensitized by Rh2b42+ and Rh4b86+, previously shown to produce H2 stoichiometrically on irradiation in strongly acidic solution, was explored. Experiments were also conducted with Rh2(TMB)42+ (TMB = 2,5-diisocyano-2,5-dimethylhexane) in the hopes of accomplishing similar energy storage reactions. The equilibria in acidic aqueous solution involving these species as well as oligomers of intermediate oxidation state were also studied. Kinetic studies of the reduction of Rh2b44+ by H2 and of thermal and photochemical oxidation of Rh4b86+ by O2 were inconclusive.
\r\n", "date": "1982", "date_type": "degree", "id_number": "CaltechETD:etd-03092005-130854", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechETD:etd-03092005-130854", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" }, { "agency": "Standard Oil Company" } ] }, "collection": "CaltechTHESIS", "reviewer": "Melissa Ray", "deposited_by": "Imported from ETD-db", "deposited_on": "2005-03-09", "doi": "10.7907/PBEA-8W62", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "chair" }, { "id": "Marsh-R-E", "name": { "family": "Marsh", "given": "Richard Edward" }, "role": "member" }, { "email": "dadougherty@caltech.edu", "id": "Dougherty-D-A", "name": { "family": "Dougherty", "given": "Dennis A." }, "role": "member" }, { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" }, { "email": "wag@caltech.edu", "id": "Goddard-W-A-III", "name": { "family": "Goddard", "given": "William A., III" }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_submitted_date": "2005-03-09", "thesis_defense_date": "1981-09-04", "thesis_approved_date": "2005-03-09", "thesis_awards": "The Herbert Newby McCoy Award, 1981", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive\nlicense to archive and make accessible, under the conditions specified below,\nmy thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1982", "author_list": "Maverick, Andrew William", "advisor_list": "Bercaw, John E.", "comittee_list": "Gray, Harry B.; Marsh, Richard Edward; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/767", "eprint_id": 767, "rev_number": 33, "documents": [ { "id": "/id/document/1144", "doc_id": 1144, "rev_number": 3, "files": [ { "id": "/id/file/7188", "fileid": 7188, "datasetid": "document", "objectid": 1144, "filename": "Smith_tp_1982.pdf", "mime_type": "application/pdf", "filesize": 3284676, "mtime": "2012-12-26 02:32:14", "url": "/767/1/Smith_tp_1982.pdf" } ], "eprint_id": 767, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "format_desc": "Original (no OCR) Smith_tp_1982.pdf", "language": "en", "security": "internal", "license": "other", "main": "Smith_tp_1982.pdf", 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"media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/110458" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/110458" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/110458" } ] } } ], "eprint_status": "archive", "userid": 2, "dir": "disk0/00/00/07/67", "datestamp": "2009-02-26", "lastmod": "2021-04-16 22:15:30", "status_changed": "2009-09-25 01:46:03", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Smith-Terrance-Patrick", "name": { "family": "Smith", "given": "Terrance Patrick" }, "show_email": "NO" } ] }, "title": "Syntheses and Characterization of a Series of Binuclear Iridium Complexes", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "A binuclear iridium(I) isocyanide complex has been synthesized and its photophysics and chemistry have been synthesized and its photophysics and chemistry have been investigated. The complex Ir2(TMB)2+4 (TMB = 2.5-dimethyl 2,5 diisocyanohexane), possesses an intense absorption band maximizing at 625 nm in the visible region. Excitation into this feature results in two long wavelength luminescence bands at 735 nm and 1080 nm. The longer wavelength feature has been assigned as phosphorescence (E(3A2) \u2192 A1(1A1)) from the lowest electronic excited state; the lifetime of this state is 200 ns and is independent of temperature between 77 K and 298 K. In contrast, the E(3A2) excited state of the analogous rhodium complex exhibits a dramatic temperature dependence. This difference is ascribed to the proximity of ligand field states to the lowest excited state; in the rhodium case the ligand field states are thermally accessible whereas for the iridium case they lie at much higher energy.
\r\n\r\nThe d8 - d8 iridium complex oxidatively adds a variety of small molecules (e.g. I2, Br2, Cl2, CH3I, HCl). The reactivity is quite similar to that of the analogous rhodium system (Rh2(TMB)2+4). One interesting difference is the fact that the HC1 adduct of Rh2(TMB)2+4 is directly observable only at low temperature. Nonetheless, a similar hydride species is postulated as an important intermediate in the production of hydrogen in another binuclear rhodium system.
\r\n\r\nA number of spectroscopic methods have been employed to explore the bonding in symmetric oxidative addition adducts. A linear correlation between metal-metal-force constant and intermetallic distance has been uncovered. The structure of the iodine adduct, Ir2(TMB)4I2(BPh4)2, has been determined; the intermetallic distance 2.803(4) \u00c5. Also dynamic 1H NMR reveals that binuclear complexes containing the TMB ligand are rapidly undergoing conformation changes at ambient temperatures; the activation barriers for this process range from 12 to 15 kcal/mole.
", "date": "1982", "date_type": "degree", "id_number": "CaltechETD:etd-02252009-153626", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechETD:etd-02252009-153626", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Melissa Ray", "deposited_by": "Imported from ETD-db", "deposited_on": "2009-02-26", "doi": "10.7907/xc18-n193", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "chair" }, { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "member" }, { "id": "Janda-K-C", "name": { "family": "Janda", "given": "Kenneth C." }, "role": "member" }, { "id": "Marsh-R-E", "name": { "family": "Marsh", "given": "Richard Edward" }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_submitted_date": "2009-02-25", "thesis_defense_date": "1982-03-08", "thesis_approved_date": "2009-02-26", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive\nlicense to archive and make accessible, under the conditions specified below,\nmy thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1982", "author_list": "Smith, Terrance Patrick", "advisor_list": "Bercaw, John E.", "comittee_list": "Bercaw, John E.; Gray, Harry B.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/10778", "eprint_id": 10778, "rev_number": 17, "documents": [ { "id": "/id/document/87283", "doc_id": 87283, "rev_number": 3, "files": [ { "id": "/id/file/247680", "fileid": 247680, "datasetid": "document", "objectid": 87283, "filename": "Thiel_PA_1981.pdf", "mime_type": "application/pdf", "hash": "583e54304142fc36b4f46f80fccc9751", "hash_type": "MD5", "filesize": 148736950, "mtime": "2018-03-22 21:24:27", "url": "/10778/1/Thiel_PA_1981.pdf" } ], "eprint_id": 10778, "pos": 1, "placement": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", 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"/id/document/87283" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/87283" } ] } } ], "eprint_status": "archive", "userid": 8820, "dir": "disk0/00/01/07/78", "datestamp": "2018-03-27 17:13:52", "lastmod": "2021-04-16 22:56:18", "status_changed": "2018-03-27 17:13:52", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Thiel-Patricia-Ann", "name": { "family": "Thiel", "given": "Patricia Ann" } } ] }, "title": "Adsorption, Co-Adsorption and Catalytic Reactions on Rh(111) and Ru(001) Surfaces", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "The adsorption of oxygen, hydrogen, carbon monoxide , nitric oxide and water on Rh(111) and Ru(001) surfaces has been studied using the techniques of high-resolution electron energy loss spectroscopy, low-energy electron diffraction, Auger electron spectroscopy, ultraviolet photoelectron spectroscopy and thermal desorption mass spectrometry. In many cases co-adsorption experiments have provided insight into the nature of interaction between different adsorbates, with potential implications for heteroqeneous catalytic reaction mechanisms.
\r\n\r\nThe interaction of oxygen with Rh(111) consists of adsorption, irreversible thermally induced ordering and disordering phenomena, dissolution into the subsurface region and desorption. The thermodynamic parameters which describe these phenomena have been investigated. The forms of the kinetic rate expressions for the catalytic reaction of adsorbed oxygen with hydrogen are different for ordered and disordered arrays of oxygen adatoms. In agreement with co-adsorption studies of hydrogen and oxygen, and supported by studies of hydrogen chemisorption on clean Rh(111), this implies that the rate of adsorption of hydrogen is sensitive to the structure of the adsorbed oxygen lattice.
\r\n\r\nTwo forms of molecularly adsorbed NO are readily distinguished on a Ru(001) surface by the frequencies of the nitrogen-oxygen stretching vibrations, which can then be used to observe the influence of co-adsorbates. Oxygen, nitrogen and hydrogen adatoms compete selectively for the adsites which are occupied by multiply-coordinated NO, whereas CO competes for adsites occupied by the singly-coordinated molecular NO. Carbon monoxide can even induce conversion of adsorbed molecular NO from sites of single coordination to sites of multiple coordination with the metal substrate.
\r\n\r\nWater interacts with the Ru(001) surface to form chemisorption bonds, but it also forms intermolecular hydrogen bonds which are of comparable strength. This leads to formation of layered, hydrogen bonded aggregates at all coverages. The properties of the first two layers are distinct from those of the subsequent ice multilayers, and a specific structural model for the hydrogen bonded lattices is proposed. A thermally induced ordering effect is observed which is analogous to the vitreous-to-cubic phase transformation of bulk ice.
", "date": "1981", "date_type": "degree", "id_number": "CaltechTHESIS:03222018-134525550", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:03222018-134525550", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" }, { "agency": "IBM" }, { "agency": "American Vacuum Society" } ] }, "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "deposited_by": "Mel Ray", "deposited_on": "2018-03-27 17:13:52", "doi": "10.7907/8m9w-p414", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "chair" }, { "id": "Weinberg-W-H", "name": { "family": "Weinberg", "given": "William Henry" }, "role": "member" }, { "email": "wag@wag.caltech.edu", "id": "Goddard-W-A-III", "name": { "family": "Goddard", "given": "William A., III" }, "role": "member" }, { "id": "Kuppermann-A", "name": { "family": "Kuppermann", "given": "Aron" }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1980-12-01", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1981", "author_list": "Thiel, Patricia Ann", "advisor_list": "Bercaw, John E.", "comittee_list": "Bercaw, John E.; Weinberg, William Henry; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/16230", "eprint_id": 16230, "rev_number": 13, "documents": [ { "id": "/id/document/140517", "doc_id": 140517, "rev_number": 3, "files": [ { "id": "/id/file/419844", "fileid": 419844, "datasetid": "document", "objectid": 140517, "filename": "Threlkel_R_1980.zip", "mime_type": "application/zip", "hash": "9b5856cff30ddc6038d59e6359fe09c1", "hash_type": "MD5", "filesize": 96940715, "mtime": "2023-10-31 22:29:39", "url": "/16230/1/Threlkel_R_1980.zip" } ], "eprint_id": 16230, "pos": 1, "placement": 1, "mime_type": "application/zip", "format": "application/zip", "format_desc": "TIFF files", "language": "en", "security": "internal", "license": "other", "main": "Threlkel_R_1980.zip", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "archival" }, { "id": "/id/document/140520", "doc_id": 140520, "rev_number": 2, "files": [ { "id": "/id/file/419858", "fileid": 419858, "datasetid": "document", "objectid": 140520, "filename": "Threlkel_R_1980.pdf", "mime_type": "application/pdf", "hash": "25fb962df7283dd949d69465e3c011c1", "hash_type": "MD5", "filesize": 31470801, "mtime": "2023-10-31 22:42:53", "url": "/16230/2/Threlkel_R_1980.pdf" } ], "eprint_id": 16230, "pos": 2, "placement": 2, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": "Threlkel_R_1980.pdf", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "final" }, { "id": "/id/document/140523", "doc_id": 140523, "rev_number": 1, "files": [ { "id": "/id/file/419874", "fileid": 419874, "datasetid": "document", "objectid": 140523, "filename": "indexcodes.txt", "mime_type": "text/plain", "hash": "7a85c90fc0620e266005305c6da2e577", "hash_type": "MD5", "filesize": 19664, "mtime": "2023-10-31 22:50:10", "url": "/16230/3/indexcodes.txt" } ], "eprint_id": 16230, "pos": 3, "placement": 3, "mime_type": "text/plain", "format": "other", "format_desc": "Generate index codes conversion from application/pdf to indexcodes", "language": "en", "security": "public", "license": "other", "main": "indexcodes.txt", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/140520" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/140520" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/140520" } ] } } ], "eprint_status": "archive", "userid": 34, "dir": "disk0/00/01/62/30", "datestamp": "2023-10-31 22:45:00", "lastmod": "2023-10-31 22:45:24", "status_changed": "2023-10-31 22:45:00", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Threlkel-Richard-S", "name": { "family": "Threlkel", "given": "Richard S." }, "show_email": "NO" } ] }, "title": "Early Transition Metal Organometallic Reactivity. Catalytic Acetylene Hydrogenation and Dimerization. Carbene Migratory Insertion Reactions", "ispublished": "unpub", "full_text_status": "public", "keywords": "(Chemistry)", "abstract": "[Not transcribed]", "date": "1980", "date_type": "degree", "id_number": "CaltechTHESIS:10312023-222717548", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:10312023-222717548", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "deposited_by": "Kathy Johnson", "deposited_on": "2023-10-31 22:45:00", "doi": "10.7907/ay0x-zs17", "alt_title": { "items": [ "Catalytic Acetylene Hydrogenation and Dimerization", "Carbene Migratory Insertion Reactions" ] }, "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "name": { "family": "Unknown", "given": "Unknown" } } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1980-02-04", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1980", "author_list": "Threlkel, Richard S.", "advisor_list": "Bercaw, John E.", "comittee_list": "Unknown, Unknown" }, { "id": "https://thesis.library.caltech.edu/id/eprint/5683", "eprint_id": 5683, "rev_number": 14, "documents": [ { "id": "/id/document/9790", "doc_id": 9790, "rev_number": 5, "files": [ { "id": "/id/file/62689", "fileid": 62689, "datasetid": "document", "objectid": 9790, "filename": "Auburn_pr_1980.pdf", "mime_type": "application/pdf", "filesize": 778746, "mtime": "2012-12-26 03:24:08", "url": "/5683/1/Auburn_pr_1980.pdf" } ], "eprint_id": 5683, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": "Auburn_pr_1980.pdf", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "final", "relation": { "items": [ { "type": "http://eprints.org/relation/hasVolatileVersion", "uri": "/id/document/25697" }, { "type": "http://eprints.org/relation/haspreviewThumbnailVersion", "uri": "/id/document/25697" }, { "type": "http://eprints.org/relation/hasVersion", "uri": "/id/document/25697" } ] } }, { "id": "/id/document/13254", "doc_id": 13254, "rev_number": 3, "files": [ { "id": "/id/file/205292", "fileid": 205292, "datasetid": "document", "objectid": 13254, "filename": "Auburn_pr_1980.zip", "mime_type": "application/zip", "filesize": 1544006, "mtime": "2016-08-22 21:19:01", "url": "/5683/2/Auburn_pr_1980.zip" } ], "eprint_id": 5683, "pos": 2, "format": "application/zip", "format_desc": "TIFF", "language": "en", "security": "internal", "license": "other", "main": "Auburn_pr_1980.zip", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "final" }, { "id": "/id/document/25697", "doc_id": 25697, "rev_number": 3, "files": [ { "id": "/id/file/62687", "fileid": 62687, "datasetid": "document", "objectid": 25697, "filename": "preview.png", "mime_type": "image/png", "hash": "cdbf9645874b1940ea82158bff73d435", "hash_type": "MD5", "filesize": 10191, "mtime": "2012-12-26 03:24:08", "url": "/5683/3/preview.png" } ], "eprint_id": 5683, "pos": 3, "placement": 3, "mime_type": "image/png", "format": "image/png", "language": "en", "security": "public", "license": "other", "main": "preview.png", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/9790" }, { "type": "http://eprints.org/relation/ispreviewThumbnailVersionOf", "uri": "/id/document/9790" }, { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/9790" } ] } } ], "eprint_status": "archive", "userid": 51, "dir": "disk0/00/00/56/83", "datestamp": "2010-04-19 16:19:11", "lastmod": "2021-04-16 22:23:42", "status_changed": "2010-04-19 16:19:11", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Auburn-P-R", "name": { "family": "Auburn", "given": "Pamela R." }, "show_email": "NO" } ] }, "title": "Synthesis, characterization, and reactivity of permethyltitanocene monoethylene complex", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "No abstract.", "date": "1980", "date_type": "degree", "id_number": "CaltechTHESIS:04022010-140317486", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:04022010-140317486", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Gayle Hammer", "deposited_by": "Tony Diaz", "deposited_on": "2010-04-19 16:19:11", "doi": "10.7907/q8e0-k091", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "masters", "thesis_advisor": { "items": [ { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "name": { "family": "Unknown", "given": "Unknown" } } ] }, "thesis_degree": "MS", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1979-08-01", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1980", "author_list": "Auburn, Pamela R.", "advisor_list": "Bercaw, John E.", "comittee_list": "Unknown, Unknown" }, { "id": "https://thesis.library.caltech.edu/id/eprint/14078", "eprint_id": 14078, "rev_number": 19, "documents": [ { "id": "/id/document/114482", "doc_id": 114482, "rev_number": 2, "files": [ { "id": "/id/file/351134", "fileid": 351134, "datasetid": "document", "objectid": 114482, "filename": "Schweizer_A_1974.pdf", "mime_type": "application/pdf", "hash": "aaae5d4f05ee9ff72b6dc6e580775ab4", "hash_type": "MD5", "filesize": 32767791, "mtime": "2021-02-08 22:12:16", "url": "/14078/1/Schweizer_A_1974.pdf" } ], "eprint_id": 14078, "pos": 1, "placement": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": "Schweizer_A_1974.pdf", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "final" }, { "id": "/id/document/114483", "doc_id": 114483, "rev_number": 4, "files": [ { "id": "/id/file/351136", "fileid": 351136, "datasetid": "document", "objectid": 114483, "filename": "Schweizer_A_1974.zip", "mime_type": "application/zip", "hash": "489e9444032554ca29a32531cc1dc559", "hash_type": "MD5", "filesize": 87354683, "mtime": "2021-02-08 22:12:34", "url": "/14078/2/Schweizer_A_1974.zip" } ], "eprint_id": 14078, "pos": 2, "placement": 2, "mime_type": "application/zip", "format": "application/zip", "format_desc": "TIFFs", "language": "en", "security": "internal", "license": "other", "main": "Schweizer_A_1974.zip", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "archival" }, { "id": "/id/document/131516", "doc_id": 131516, "rev_number": 1, "files": [ { "id": "/id/file/376955", "fileid": 376955, "datasetid": "document", "objectid": 131516, "filename": "indexcodes.txt", "mime_type": "text/plain", "hash": "337cb1c5063958f501f911436ff0c869", "hash_type": "MD5", "filesize": 19271, "mtime": "2021-06-24 18:00:37", "url": "/14078/3/indexcodes.txt" } ], "eprint_id": 14078, "pos": 3, "placement": 3, "mime_type": "text/plain", "format": "other", "format_desc": "Generate index codes conversion from application/pdf to indexcodes", "language": "en", "security": "public", "license": "other", "main": "indexcodes.txt", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/114482" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/114482" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/114482" } ] } } ], "eprint_status": "archive", "userid": 87, "dir": "disk0/00/01/40/78", "datestamp": "2021-02-09 00:11:58", "lastmod": "2021-02-09 00:12:38", "status_changed": "2021-02-09 00:11:58", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Schweizer-Albert-Edward-Jr", "name": { "family": "Schweizer", "given": "Albert Edward, Jr." }, "show_email": "NO" } ] }, "title": "Studies of Some Inorganic Reaction Mechanisms", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "note": "Title in 1974 commencement program -- Studies of Some Inorganic Reaction Mechanisms: Part I. The Isomerization of Metal Complexes in Solution. Part II. Reaction of Nitric Oxide with Cobalt Ammine Solutions. Part III. Kinetic Studies of Nitric Oxide Decomposition over a Cobalt Oxide Catalyst -- differs from title in thesis file (PDF).", "abstract": "Part I
\r\n\r\nThe compound dihydridotetrakis (diethylphenylphosphonite)-iron(II) is known to undergo rapid rearrangement in solution. Considerable discussion has been presented to formulate a mechanism for this rearrangement. This discussion is based on a rearrangement between cis and trans dihydride isomers of octahedral stereochemistry. We present here some experimental evidence which shows the identification of one isomer (as the trans dihydride) is incorrect and also that the changes that occur are more complicated than the earlier workers proposed. Infrared, Raman, and very low temperature 1H n. m. r. spectra of both the iron and ruthenium compounds are used to construct a different picture of this system. We identify three distinct reactions or rearrangements that are occurring and offer some proposals for the structures of the isomers. A non-classical six-coordinate structure based on a tetrahedral skeleton of phosphorus atoms about the central metal is considered the most reasonable identification of the non-cis isomer.
\r\n\r\nPart II
\r\n\r\nNitric oxide undergoes many reactions to form transition metal nitrosyls of varying geometry. Under very special conditions, it then continues to react to form a species with nitrogen to nitrogen bonds. We have studied one of these reactions in detail: First, to establish the stoichiometry of the reaction exactly and second, to gain some insight into the mechanism of the dimerization step.
\r\n\r\nThere is an initial rapid reaction of an ammoniacal Co(II) solution and NO with the stoichiometry one NO per cobalt(II). The NO pressure dependence of the ratio NO to cobalt is given experimentally. A qualitative proposal is made to explain this dependence, but we are still searching for a quantitative description.
\r\n\r\nThere is a much slower reaction that consumes additional nitric oxide, producing N2O and nitrite ions. If the initial cobalt(II) concentration is high, an additional product is obtained, the \u03bc-hyponitrito bis(pentaammine cobalt(III)) ion, usually precipitated as the nitrate. The yield of the dimeric cation as a function of concentration, anion, and temperature are given. A proposal of a linkage isomerization of an unstable dimer of pentaamminenitrosyl cobalt(III) is offered to explain the experimental observations.
\r\n\r\nPart III
\r\n\r\nThe decomposition of nitric oxide to elements in the gas phase is a thermodynamically favored reaction that is very slow at low temperatures (below 1000\u00b0K). Some catalysts are known for this reaction carried out in a heterogeneous reactor. Work has been performed jointly with the chemical engineering faculty to try to understand the reaction over one of the known catalysts. The rate limiting factor is shown to be the strong inhibition by the product oxygen rather than any intrinsically slow reaction of NO. An interpretation of both our results and the results of another group is offered in terms of a unimolecular decomposition on a surface.
", "date": "1974", "date_type": "degree", "id_number": "CaltechTHESIS:02082021-221037462", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:02082021-221037462", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Mobil Research and Development Corporation" }, { "agency": "Caltech" } ] }, "collection": "CaltechTHESIS", "reviewer": "Melissa Ray", "deposited_by": "Benjamin Perez", "deposited_on": "2021-02-09 00:11:58", "doi": "10.7907/75es-0c18", "alt_title": { "items": [ "Studies of Some Inorganic Reaction Mechanisms: Part I. The Isomerization of Metal Complexes in Solution. Part II. Reaction of Nitric Oxide with Cobalt Ammine Solutions. Part III. Kinetic Studies of Nitric Oxide Decomposition over a Cobalt Oxide Catalyst", "The Isomerization of Metal Complexes in Solution", "Reaction of Nitric Oxide with Cobalt Ammine Solutions", "Kinetic Studies of Nitric Oxide Decomposition over a Cobalt Oxide Catalyst" ] }, "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "advisor" }, { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "co-advisor" } ] }, "thesis_committee": { "items": [ { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "member" }, { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1973-06-29", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1974", "author_list": "Schweizer, Albert Edward, Jr.", "advisor_list": "Gray, Harry B. and Bercaw, John E.", "comittee_list": "Gray, Harry B. and Bercaw, John E." } ]