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"2023-09-28 20:46:48", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "nick.b.watkins@gmail.com", "id": "Watkins-Nicholas-B", "name": { "family": "Watkins", "given": "Nicholas B." }, "orcid": "0000-0001-7251-9387", "show_email": "YES" } ] }, "title": "Organic Films at the Electrode-Electrolyte Interface in CO\u2082 Reduction", "ispublished": "unpub", "full_text_status": "restricted", "keywords": "CO2 reduction; electrochemistry; electrocatalysis", "abstract": "This thesis focuses on the use of use high-throughput experimentation and analytical electrochemistry techniques to understand how organic films on (photo)electrode surfaces alter catalyst selectivity. Specifically, the objective has been to deconvolute effects associated with the organic film from the atomic identity of the catalyst, reactant and intermediate concentration polarization effects, and temperature in the context of electrochemical CO\u2082 reduction. The first chapter provides the motivations behind the transformation of CO\u2082 into value-added materials using electricity and the challenges that the field faces. The second chapter introduces the data-driven identification of a scaling relationship between the partial current densities of methane and C\u2082\u208a products among 14 bulk copper bimetallic alloys. This strict dependence represents an intrinsic limitation of selectivity tuning through alloying. However, it can be disrupted to favor C\u2082\u208a products by the presence of an organic additive, highlighting the potential of hybrid organic\u2013inorganic catalysts to tune branching ratios in the CO\u2082R reaction network. The third chapter highlights that with the wide band gap CuGa\u2083Se\u2085 chalcopyrite absorber, organic coatings can not only provide dramatic increases in selectivity toward CO\u2082R products compared to the unmodified system, but also and significantly moderate catalyst corrosion. The fourth chapter unveils a new class of molecular films on polycrystalline copper, derived from aryl diazonium and iodonium salts, that are corrosion resistant even at pH 1 and have the potential for many future electrochemical applications. In the fifth chapter, we demonstrate that increased mass transport at the electrode surface directly resulted in changes to the ethylene and methane Tafel slope values on copper electrodes. These findings emphasize that the apparent Tafel slope reported for any copper system is not necessarily representative of the catalyst\u2019s intrinsic kinetics alone, but also contains information about the cell geometry and electrolyte convective transport. The final chapter investigates the combined effect of organic films, mass transport, and electrode heating on electrocatalysis. We find that we can use surface heating to replace bulk heating, but that the complexity of CO\u2082R prevents predictable behavior. However, the addition of additive films to the electrode surface enables idealized electrochemical CO\u2082 reduction kinetics, and therefore the calculation of important parameters such as the activation energy for C\u2082\u208a product formation.", "date": "2024", "date_type": "degree", "id_number": "CaltechTHESIS:09272023-154324412", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:09272023-154324412", "related_url": { "items": [ { "description": "Article adapted for Chapter 2, Appendix 2", "type": "doi", "url": "https://pubs.acs.org/doi/full/10.1021/acscentsci.1c00860" }, { "description": "Article adapted for Chapter 3, Appendix 3", "type": "doi", "url": "https://pubs.acs.org/doi/full/10.1021/acsenergylett.1c02762" }, { "description": "Article adapted for Chapter 4, Appendix 4", "type": "doi", "url": "https://pubs.acs.org/doi/full/10.1021/acsenergylett.2c02002" }, { "description": "Article adapted for Chapter 5, Appendix 5", "type": "doi", "url": "https://pubs.acs.org/doi/full/10.1021/acsenergylett.3c00442" } ] }, "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Department of Energy (DOE)", "grant_number": "DE-SC0021266" } ] }, "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "suggestions": "Restricted to campus until 28 March 2024", "deposited_by": "Nicholas Watkins", "deposited_on": "2023-09-28 20:46:48", "doi": "10.7907/7t8e-7j20", "alt_title": { "items": [ "Organic Films at the Electrode-Electrolyte Interface in CO2 Reduction" ] }, "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "jpeters@caltech.edu", "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414", "role": "co-advisor" }, { "email": "gregoire@caltech.edu", "id": "Gregoire-J-M", "name": { "family": "Gregoire", "given": "John M." }, "orcid": "0000-0002-2863-5265", "role": "co-advisor" } ] }, "thesis_committee": { "items": [ { "email": "ksee@caltech.edu", "id": "See-Kimberly", "name": { "family": "See", "given": "Kimberly" }, "orcid": "0000-0002-0133-9693", "role": "chair" }, { "email": "reisman@caltech.edu", "id": "Reisman-S-E", "name": { "family": "Reisman", "given": "Sarah E." }, "orcid": "0000-0001-8244-9300", "role": "member" }, { "email": "karthish@caltech.edu", "id": "Manthiram-Karthish", "name": { "family": "Manthiram", "given": "Karthish" }, "orcid": "0000-0001-9260-3391", "role": "member" }, { "email": "jpeters@caltech.edu", "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414", "role": "member" }, { "email": "gregoire@caltech.edu", "id": "Gregoire-J-M", "name": { "family": "Gregoire", "given": "John M." }, "orcid": "0000-0002-2863-5265", "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "2023-09-20", "gradofc_approval_date": "2023-03-28", "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": "2024", "author_list": "Watkins, Nicholas B.", "advisor_list": "Peters, Jonas C. and Gregoire, John M.", "comittee_list": "See, Kimberly; Reisman, Sarah E.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/15147", "eprint_id": 15147, "rev_number": 97, "documents": [ { "id": "/id/document/138434", "doc_id": 138434, "rev_number": 6, "files": [ { "id": "/id/file/405546", "fileid": 405546, "datasetid": "document", "objectid": 138434, "filename": "zott_thesis.pdf", "mime_type": "application/pdf", "hash": "b078a6380707e57f6a055ae9b62543cc", "hash_type": "MD5", "filesize": 19270979, "mtime": "2023-04-28 21:08:02", "url": "/15147/1/zott_thesis.pdf" } ], "eprint_id": 15147, "pos": 1, "placement": 1, "mime_type": "application/pdf", "format": "application/pdf", "format_desc": "Full Thesis", "language": 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"MD5", "filesize": 51618988, "mtime": "2023-05-05 00:39:05", "url": "/15147/21/thesis_source_zott.zip" } ], "eprint_id": 15147, "pos": 21, "placement": 21, "mime_type": "application/zip", "format": "application/zip", "format_desc": "Source files", "language": "en", "security": "internal", "license": "other", "main": "thesis_source_zott.zip", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "archival" } ], "eprint_status": "archive", "userid": 12929, "dir": "disk0/00/01/51/47", "datestamp": "2023-05-15 20:23:57", "lastmod": "2023-11-08 00:44:04", "status_changed": "2023-05-15 20:23:57", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "mdzott18@gmail.com", "id": "Zott-Michael-David", "name": { "family": "Zott", "given": "Michael David" }, "orcid": "0000-0003-0535-0512", "show_email": "NO" } ] }, "title": "Strategic Applications of Electrochemistry in Ammonia Oxidation and Alkyl Halide Reduction", "ispublished": "unpub", "full_text_status": "public", "keywords": "electrocatalysis; ammonia oxidation; nitrogen reduction; photocatalysis; single-electron reduction", "abstract": "This thesis describes the strategic application of electrochemistry in the development of catalytic systems for two challenging processes: alkyl halide reduction and ammonia oxidation. In the case of alkyl halide reduction, the ability to precisely tune electrochemical potential favored the use of electrochemistry as compared to chemical reagents. By contrast, for ammonia oxidation, electrochemistry was specifically targeted due to motivations in the eventual development of ammonia fuel cell technology. The first chapter introduces these and other advantages of electrochemistry, as well as details regarding the thermodynamic potentials and kinetic barriers associated with alkyl halide reduction or ammonia oxidation. The second chapter details our development of photoelectrochemical methodology to employ a strongly luminescent dicopper system for outer-sphere, single-electron transfer reduction of benzyl chlorides. The third chapter marks the beginning of our work in molecular iron-mediated ammonia oxidation catalysis, in which we develop our hypothesis that catalyst structures featuring cis-labile coordination sites should mediate ammonia oxidation. We disclose the first iron electrocatalyst ([(TPA)Fe(MeCN)\u2082]\u00b2\u207a) as well as a framework for the analysis of metrics such as overpotential, catalytic rate, and catalyst stability. The fourth chapter introduces a hypothesis for catalyst improvement\u2014favoring low-spin electronic structures\u2014and a model system for testing: ([(BPM)Fe(MeCN)\u2082]\u00b2\u207a). Using this second-generation catalyst, improved stability, enhanced activity, and lowered overpotential were observed. The fifth chapter explores the validity of the cis-labile and low-spin hypotheses via Hammett-type substituent studies on both the [(TPA)Fe(MeCN)\u2082]\u00b2\u207a and the [(BPM)Fe(MeCN)\u2082]\u00b2\u207a platforms. This study resulted in the development of a further enhanced molecular electrocatalyst for ammonia oxidation and revealed mechanistic information pertinent to the development of future catalytic systems.", "date": "2023", "date_type": "degree", "id_number": "CaltechTHESIS:04282023-205948012", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:04282023-205948012", "related_url": { "items": [ { "description": "Article for chapter 2", "type": "doi", "url": "https://doi.org/10.1021/acscatal.2c03215" }, { "description": "Article for chapter 3", "type": "doi", "url": "https://doi.org/10.1021/acscatal.9b03499" }, { "description": "Article for chapter 4", "type": "doi", "url": "https://doi.org/10.1021/jacs.1c02232" } ] }, "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Resnick Sustainability Institute Graduate Research Fellowship" }, { "agency": "NSF Graduate Research Fellowship", "grant_number": "1745301" }, { "agency": "NIH", "grant_number": "R01-109194" }, { "agency": "NIH", "grant_number": "GM070757" }, { "agency": "Department of Energy (DOE)", "grant_number": "0235032" } ] }, "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "suggestions": "Released 2023-05-22. 1-week embargo until 22 May 2023.", "deposited_by": "Michael Zott", "deposited_on": "2023-05-15 20:23:57", "doi": "10.7907/4fr8-7r78", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "jpeters@caltech.edu", "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414", "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "rghadt@caltech.edu", "id": "Hadt-Ryan-G", "name": { "family": "Hadt", "given": "Ryan G." }, "orcid": "0000-0001-6026-1358", "role": "chair" }, { "email": "jpeters@caltech.edu", "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414", "role": "member" }, { "email": "gkc1000@gmail.com", "id": "Chan-G-K", "name": { "family": "Chan", "given": "Garnet K." }, "orcid": "0000-0001-8009-6038", "role": "member" }, { "email": "gcfu@caltech.edu", "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X", "role": "member" }, { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876", "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "2023-02-28", "gradofc_approval_date": "2023-05-12", "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": "2023", "author_list": "Zott, Michael David", "advisor_list": "Peters, Jonas C.", "comittee_list": "Hadt, Ryan G.; Peters, Jonas C.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/14402", "eprint_id": 14402, "rev_number": 41, "documents": [ { "id": "/id/document/135172", "doc_id": 135172, "rev_number": 4, "files": [ { "id": "/id/file/384592", "fileid": 384592, "datasetid": "document", "objectid": 135172, "filename": "Dirk Schild Thesis Final.docx", "mime_type": "application/vnd.openxmlformats-officedocument.wordprocessingml.document", "hash": "b1edc93df3ec69786a7c5b503ac3e8e9", "hash_type": "MD5", "filesize": 55203272, "mtime": "2021-10-19 16:23:41", "url": "/14402/2/Dirk Schild Thesis Final.docx" } ], "eprint_id": 14402, "pos": 2, "placement": 2, "mime_type": 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Mitigating the hydrogen evolution (HER) is an outstanding challenge in small molecule reduction catalysis using protons and electrons. Nitrogen fixation is a fundamental reaction where this selectivity is of great importance. This thesis details mechanistic studies into the nitrogen fixation reaction and factors that contribute to hydrogen evolution. In addition to the mechanistic studies, the development of reagents with weak X-H bonds, with applications in N-H bond formation is presented. Chapter 1 presents a brief overview of catalytic nitrogen fixation, the role of hydride ligands, and the importance of reagents required for the formation of weak N-H bonds. Chapter 2 details the mechanism of photo-enhanced iron mediated N2 fixation. It is shown that off-path iron complexes bearing hydride ligands play an active role in hydrogen evolution by N2 fixation catalysts. The data presented lends further insight into the selectivity, activity, and required driving force relevant to iron (and other) N2RR catalysts. The third chapter describes the synthesis and characterization of a highly reactive iron(III) nitrido complex, a proposed key intermediate in nitrogen fixation mediated by [(P3B)Fe]+. The ability to synthesize and characterize such an intermediate provides additional support for a distal catalytic cycle for this catalyst. In Chapters 4 and 5, the reactivity of iron hydrides and their role as precursors towards weak C-H bonds is discussed. These chapters outline a valuable approach for the differentiation of a ring- versus a metal bound H-atom. Chapter 4 provides a structural, thermochemical, and mechanistic foundation for the characterization of ring protonated indene-based ligands with remarkably weak C-H bonds. Chapter 5 extends the characterization of such reactive species and presents ligand induced migration of the hydride to a Cp* ring.
", "date": "2022", "date_type": "degree", "id_number": "CaltechTHESIS:10192021-161648176", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:10192021-161648176", "related_url": { "items": [ { "description": "Published content for Chapter 2.", "type": "doi", "url": "https://doi.org/10.1021/acscatal.9b00523" }, { "description": "Published content for Chapter 4.", "type": "doi", "url": "https://doi.org/10.1002/anie.201909050" }, { "description": "Published content for Chapter 5.", "type": "doi", "url": "https://doi.org/10.1021/jacs.0c09363" } ] }, "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Melissa Ray", "suggestions": "Released to public view 20230925. // Restriction to campus until 19 October 2022 // From author: The thesis contains data for a yet unpublished manuscript.", "deposited_by": "Dirk Schild", "deposited_on": "2022-04-20 19:41:47", "doi": "10.7907/1ytm-7s85", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "jpeters@caltech.edu", "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414", "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "agapie@caltech.edu", "id": "Agapie-T", "name": { "family": "Agapie", "given": "Theodor" }, "orcid": "0000-0002-9692-7614", "role": "chair" }, { "email": "tfm@caltech.edu", "id": "Miller-T-F", "name": { "family": "Miller", "given": "Thomas F." }, "orcid": "0000-0002-1882-5380", "role": "member" }, { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876", "role": "member" }, { "email": "jpeters@caltech.edu", "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414", "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "2021-09-27", "gradofc_approval_date": "2022-04-19", "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": "2022", "author_list": "Schild, Dirk Jacob", "advisor_list": "Peters, Jonas C.", "comittee_list": "Agapie, Theodor; Miller, Thomas F.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/13634", "eprint_id": 13634, "rev_number": 44, "documents": [ { "id": "/id/document/106144", "doc_id": 106144, "rev_number": 7, "files": [ { "id": "/id/file/324672", "fileid": 324672, "datasetid": "document", "objectid": 106144, "filename": "MatthewJChalkley_Thesis_Final.pdf", "mime_type": "application/pdf", "hash": "0e7046eac107df2b3ec6a25e936f0e3a", "hash_type": "MD5", "filesize": 17710230, "mtime": "2020-02-06 20:54:11", "url": "/13634/7/MatthewJChalkley_Thesis_Final.pdf" } ], "eprint_id": 13634, "pos": 7, "placement": 7, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": 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"given": "Matthew J." }, "orcid": "0000-0002-0484-7335", "show_email": "NO" } ] }, "title": "Proton-Coupled Electron Transfer in Nitrogen Fixation", "ispublished": "unpub", "full_text_status": "public", "keywords": "Proton-coupled electron transfer, nitrogen fixation, electrocatalysis", "abstract": "This thesis focuses on the management of protons and electrons in the formation of X\u2212H bonds. In our pursuit of better understanding this process, we have been particularly interested in the nitrogen fixation reaction (N2-to-NH3) because of the high number of protons and electrons involved in this conversion (6) and the significant difficulty of functionalizing N2. The first chapter introduces the important themes of this thesis: (i) multiple bonding, (ii) proton-coupled electron transfer, (iii) overpotential in N2 fixation, and (iv) selectivity in N2 fixation. The second chapter discusses the bonding of an iron complex with a small molecule (NO) and how this bonding is key to activating the small molecule for reactivity. The third chapter looks at how employing a new proton and electron source allows an Fe catalyst to achieve improved selectivity and turnover number for the reduction of N2 to NH3 despite a lowered overpotential relative to previous reactions. It also raises the hypothesis that this is possible due to proton-coupled electron transfer mediated by a metallocene. The fourth chapter studies the effect of acid strength on N2 fixation selectivity and demonstrates circumstantial evidence for the involvement of a decamethylcobaltocene (Cp*2Co) in the formation of N\u2212H bonds via proton-coupled electron transfer. It also highlights how the addition of co-catalytic [Cp*2Co]+ to electrochemical experiments with our Fe catalyst enabled truly electrocatalytic N2 fixation for the first time. The fifth chapter provides both atomistic detail on the protonation reactivity of Cp*2Co and experimentally verifies the prediction that this species would be an extremely strong hydrogen-atom donor. It also develops a conceptual framework to explain the uniquely weak C\u2212H bonds both homolytic and heterolytic that result from metallocene protonation and discusses their potential to play a role in not only the hydrogen evolution reaction (HER), but also the N2 fixation reaction. In the final chapter, we develop a synthetic route to a base appended cobaltocene. We demonstrate that this second-generation cobaltocene can, unlike the first generation, serve as a net hydrogen-atom donor under electrocatalytic conditions. As a demonstration of the utility of this, we use the base-appended cobaltocene for the selective, proton-coupled reduction of ketones to pinacols via a rate-determing concerted proton-electron transfer.
", "date": "2020", "date_type": "degree", "id_number": "CaltechTHESIS:02052020-203503014", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:02052020-203503014", "related_url": { "items": [ { "description": "Published content for Chapter 2.", "type": "doi", "url": "https://doi.org/10.1002/anie.201605403" }, { "description": "Published content for Chapter 3.", "type": "doi", "url": "https://doi.org/10.1021/acscentsci.7b00014" }, { "description": "Published content for Chapter 4.", "type": "doi", "url": "https://doi.org/10.1021/jacs.8b02335" }, { "description": "Published content for Chapter 5.", "type": "doi", "url": "https://doi.org/10.1021/jacs.9b00193" } ] }, "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "GM070757" }, { "agency": "Department of Energy (DOE)", "grant_number": "0235302" } ] }, "collection": "CaltechTHESIS", "reviewer": "Melissa Ray", "local_group": { "items": [ "Resnick Sustainability Institute" ] }, "suggestions": "Released to public view 13 October 2020. //\r\n// Embargo request approved 4/13/2020. Withheld until 13 October 2020. From author: We are shortly going to submit Chapter 6 to the Journal of the American Chemical Society.", "deposited_by": "Matthew Chalkley", "deposited_on": "2020-02-25 00:37:11", "doi": "10.7907/FE9D-9K14", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "jpeters@caltech.edu", "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "agapie@caltech.edu", "id": "Agapie-T", "name": { "family": "Agapie", "given": "Theodor" }, "role": "chair" }, { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "member" }, { "email": "tfm@caltech.edu", "id": "Miller-T-F", "name": { "family": "Miller", "given": "Thomas F." }, "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_defense_date": "2020-01-17", "gradofc_approval_date": "2020-02-24", "thesis_awards": "The Herbert Newby McCoy Award, 2020.", "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": "2020", "author_list": "Chalkley, Matthew J.", "advisor_list": "Peters, Jonas C.", "comittee_list": "Agapie, Theodor; Gray, Harry B.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/13672", "eprint_id": 13672, "rev_number": 50, "documents": [ { "id": "/id/document/106909", "doc_id": 106909, "rev_number": 7, "files": [ { "id": "/id/file/327854", "fileid": 327854, "datasetid": "document", "objectid": 106909, "filename": "NXG-JACSpermission-Ch2.pdf", "mime_type": "application/pdf", "hash": "278a807b0592daab6db13634155e1299", "hash_type": "MD5", "filesize": 105997, "mtime": "2020-04-10 21:20:32", "url": "/13672/1/NXG-JACSpermission-Ch2.pdf" } ], "eprint_id": 13672, "pos": 1, "placement": 3, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "internal", 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processes, including proton reduction and ammonia oxidation. Towards a greater mechanistic understanding of such transformations on well-defined model complexes, this thesis explores relevant H\u2013H and N\u2013N bond-forming reactions mediated by trivalent Fe and Ni species, as well as catalytic N\u2013N bond cleavage mediated by an open-shell VFe bimetallic complex. First, a pair of thiolate-supported, S = \u00bd iron and nickel hydrides are synthesized and spectroscopically characterized at low temperatures (Chapters 2, 3). Paramagnetic iron and nickel hydrides have been proposed as catalytic intermediates of [NiFe] hydrogenase and nitrogenase, but characterization of such molecular species are limited. For both the FeIII and NiIII hydride complexes described herein, spin delocalization onto the thiolate ligand is proposed to stabilize the formal 3+ metal oxidation state. Furthermore, both the FeIII\u2013H and NiIII\u2013H species are demonstrated to undergo the bimolecular reductive elimination of dihydrogen upon warming, albeit with distinct activation parameters consistent with different proposed pathways for H\u2013H bond formation. Chapter 4 expands upon the H\u2013H bond forming chemistry demonstrated on the Ni system to demonstrate related N\u2013N bond formation from an analogous NiIII\u2013NH2 species, resulting in the formation of a NiII2(N2H4) complex. Given the diverse mechanistic possibilities for the overall 6e-/6H+ transformation to oxidize ammonia to dinitrogen, identification of the active M(NHx) intermediate and pathway for N\u2013N bond formation is a central mechanistic question. While the homocoupling of M\u2013NH2 species to form hydrazine has been hypothesized as the key N\u2013N bond forming step in ammonia oxidation systems, stoichiometric examples of this transformation from M\u2013NH2 complexes are rare. Lastly, Chapter 5 details the synthesis of a heterobimetallic VFe complex featuring a bridging thiolate, inspired by the structure of the VFe nitrogenase cofactor. This VFe species is demonstrated to be an active catalyst for the disproportionation of hydrazine to dinitrogen and ammonia. Notably, the heterobimetallic complex is appreciably more active than monometallic analogues of the individual V and Fe sites, suggesting that bimetallic cooperativity may facilitate the observed catalysis.
", "date": "2020", "date_type": "degree", "id_number": "CaltechTHESIS:04102020-135244808", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:04102020-135244808", "related_url": { "items": [ { "description": "Published content for Chapter 2.", "type": "doi", "url": "https://doi.org/10.1021/jacs.8b02603" }, { "description": "Published content for Chapter 3.", "type": "doi", "url": "https://doi.org/10.1021/jacs.0c00712" }, { "description": "Published content for Chapter 5.", "type": "doi", "url": "https://doi.org/10.1039/C9CC00345B" } ] }, "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Department of Energy (DOE)", "grant_number": "DOE-0235032" }, { "agency": "NIH", "grant_number": "GM-070757" }, { "agency": "National Science Foundation Graduate Research Fellowship" }, { "agency": "NSF", "grant_number": "NSF-1531940" }, { "agency": "Dow Next Generation Fund" } ] }, "collection": "CaltechTHESIS", "reviewer": "Melissa Ray", "suggestions": "Released to public view 10 December 2020. //\r\n// Withheld until 02 December 2020. Approved by review committee 06022020 // From author: We are currently preparing a manuscript for submission to the Journal of the American Chemical Society regarding the unpublished work in Ch. 4.", "deposited_by": "Nina Gu", "deposited_on": "2020-05-21 16:55:33", "doi": "10.7907/8zwz-gh20", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "jpeters@caltech.edu", "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "agapie@caltech.edu", "id": "Agapie-T", "name": { "family": "Agapie", "given": "Theodor" }, "role": "chair" }, { "email": "lhw@caltech.edu", "id": "Hsieh-Wilson-L-C", "name": { "family": "Hsieh-Wilson", "given": "Linda C." }, "role": "member" }, { "email": "gcfu@caltech.edu", "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "role": "member" }, { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "2020-03-09", "gradofc_approval_date": "2020-05-21", "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": "2020", "author_list": "Gu, Nina Xiao", "advisor_list": "Peters, Jonas C.", "comittee_list": "Agapie, Theodor; Hsieh-Wilson, Linda C.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/11801", "eprint_id": 11801, "rev_number": 56, "documents": [ { "id": "/id/document/103234", "doc_id": 103234, "rev_number": 8, "files": [ { "id": "/id/file/297482", "fileid": 297482, "datasetid": "document", "objectid": 103234, "filename": "deegan-meaghan-6-month-embargo-request.pdf", "mime_type": "application/pdf", "hash": "7149fd026bf36e2ecd3e86206f97c643", "hash_type": "MD5", "filesize": 95177, "mtime": "2019-09-26 17:25:58", "url": "/11801/7/deegan-meaghan-6-month-embargo-request.pdf" } ], "eprint_id": 11801, "pos": 7, "placement": 5, "mime_type": "application/pdf", "format": "application/pdf", "format_desc": 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"Meaghan Marie" }, "orcid": "0000-0002-7633-2074", "show_email": "NO" } ] }, "title": "Small Molecule Reactivity of Trisphosphine-Supported Iron and Cobalt Complexes", "ispublished": "unpub", "full_text_status": "public", "keywords": "Iron; cobalt; carbon monoxide; dihydrogen; dinitrogen", "abstract": "The work described in this thesis emphasizes accessing novel reactivity patterns in the activation of carbon monoxide, dinitrogen, and dihydrogen by leveraging phosphine-supported iron and cobalt complexes. In Chapters 2 and 3, systems that access CO and N2 reductive functionalization from highly reduced Fe-hydride precursors are described. These systems access productive C-H and N-H bond forming steps from hydride precursors that ultimately allows for the liberation of four-electron reduced products through novel chemical pathways. Chapter 4 describes an unusual example of a terminal cobalt carbyne through the O-functionalization of a carbonyl complex. Next, in Chapter 5, we consider electronically unusual examples of dihydrogen complexes and explore their propensity for accessing H-atom and hydride transfer. Finally, to conclude, Chapter 6 details our synthetic efforts targeting the synthesis of a terminal Fe-carbide complex through the cleavage of a thiocarbonyl precursor.
", "date": "2020", "date_type": "degree", "id_number": "CaltechTHESIS:09252019-210323106", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:09252019-210323106", "related_url": { "items": [ { "description": "Published content for Chapter 2", "type": "doi", "url": "https://doi.org/10.1021/jacs.6b12444" }, { "description": "Published content for Chapter 3.", "type": "doi", "url": "https://doi.org/10.1039/C8SC02380H" }, { "description": "Published content for Chapter 4.", "type": "doi", "url": "https://doi.org/10.1039/C9CC04032C" } ] }, "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "GM070757" }, { "agency": "Department of Energy (DOE)", "grant_number": "0235032" } ] }, "collection": "CaltechTHESIS", "reviewer": "Melissa Ray", "suggestions": "Released to public view 26 May 2021. //\r\n//2nd embargo extension request pending as of 9/26/2020 / Proposed Withheld until 15 April 2021. / From author: Portions of Chapter 6 of the thesis are prepared for submission to the ACS journal Inorganic Chemistry. //\r\n\r\nEmbargo extension request approved 4/15/2020. / Withheld until 15 October 2020. / From author: Portions of Chapter 6 are being prepared for publication in an ACS journal. //\r\n\r\nOriginal embargo request approved 10/22/2019. / Withheld until 24 April 2020. / From author: Portions of Chapters 5 and 6 are both in the process of being prepared for publication in ACS journals.", "deposited_by": "Meaghan Deegan", "deposited_on": "2019-10-25 00:30:56", "doi": "10.7907/QDAW-M003", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "jpeters@caltech.edu", "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "agapie@caltech.edu", "id": "Agapie-T", "name": { "family": "Agapie", "given": "Theodor" }, "role": "chair" }, { "email": "gcfu@caltech.edu", "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "role": "member" }, { "email": "reisman@caltech.edu", "id": "Reisman-S-E", "name": { "family": "Reisman", "given": "Sarah 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_defense_date": "2019-09-04", "gradofc_approval_date": "2019-10-24", "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": "2020", "author_list": "Deegan, Meaghan Marie", "advisor_list": "Peters, Jonas C.", "comittee_list": "Agapie, Theodor; Fu, Gregory C.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/11565", "eprint_id": 11565, "rev_number": 54, "documents": [ { "id": "/id/document/99500", "doc_id": 99500, "rev_number": 4, "files": [ { "id": "/id/file/286490", "fileid": 286490, "datasetid": "document", "objectid": 99500, "filename": "Hannoun_Thesis.docx", "mime_type": "application/vnd.openxmlformats-officedocument.wordprocessingml.document", "hash": "d98410343cb3aa67b3494ae449ecf5b6", "hash_type": "MD5", "filesize": 37328223, "mtime": "2019-05-30 14:36:27", "url": "/11565/7/Hannoun_Thesis.docx" } ], "eprint_id": 11565, "pos": 7, "placement": 2, "mime_type": 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20:41:31", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "kihannoun@gmail.com", "id": "Hannoun-Kareem-Imad", "name": { "family": "Hannoun", "given": "Kareem Imad" }, "orcid": "0000-0003-3176-1104", "show_email": "NO" } ] }, "title": "Mechanistic Study of Cu-Mediated, Photoinduced C\u2013S Bond Formation and Demonstration of Electrochemical Ammonia Production by a Surface-Attached Iron Complex", "ispublished": "unpub", "full_text_status": "public", "keywords": "Nitrogen fixation, electrochemistry, photochemistry, ammonia, thiol, cross coupling", "abstract": "The worldwide reliance on fossil fuels for energy and petrochemicals poses a massive environmental hazard. Furthermore, many chemical processes rely on precious metals that have low abundance on Earth and are threatened. As the world population grows rapidly, these factors pose an increasing threat to our planet and new chemical processes are needed that employ earth-abundant catalysts and alternative chemical currencies such as light and electricity derived from renewable sources.
\r\n\r\nChapter 2 discusses an in-depth mechanistic study of the photoinduced, copper-mediated cross-coupling of aryl thiols with aryl halides. This reaction employs light energy and an earth-abundant metal to achieve bond formation through a pathway distinct from that of thermal reactions. In particular, I focus on the stoichiometric photochemistry and subsequent reactivity of a [CuI(SAr)2]\u2013 complex (Ar = 2,6-dimethylphenyl). A broad array of experimental techniques furnish data consistent with a pathway in which a photoexcited [CuI(SAr)2]-* complex undergoes SET to generate a CuII species and an aryl radical, which then couple through an in-cage radical recombination.
\r\n\r\nChapter 3 discusses the surface attachment of a P3BFe complex to a carbon electrode, and the electrochemical generation of ammonia from N2 by the surface-appended species (P3BFe = tris-phosphinoborane). Ammonia production is achieved industrially by the combination of N2 and H2, the latter of which is derived from methane with concomitant production of CO2. Alternative chemical processes, such as the use of energy derived from electricity, are vital for the decreasing the carbon footprint of ammonia production. Synthetic modification of a previously-reported P3BFe complex by addition of three pyrene substituents onto the catalyst backbone allows non-covalent attachment onto a graphite surface. The resulting functionalized electrode shows good stability towards iron desorption under highly reducing conditions, and produces 1.4 equiv NH3 per iron site. The data presented provide the first demonstration of electrochemical nitrogen fixation by a molecular complex appended to an electrode.
", "date": "2019", "date_type": "degree", "id_number": "CaltechTHESIS:05302019-070503222", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:05302019-070503222", "related_url": { "items": [ { "description": "Article adapted for Chapter 2.", "type": "doi", "url": "http://dx.doi.org/10.1039/C5SC04709A" } ] }, "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Melissa Ray", "deposited_by": "Kareem Hannoun", "deposited_on": "2019-05-31 20:41:31", "doi": "10.7907/R9EJ-KX83", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "jpeters@caltech.edu", "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "gcfu@caltech.edu", "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "role": "chair" }, { "email": "agapie@caltech.edu", "id": "Agapie-T", "name": { "family": "Agapie", "given": "Theodor" }, "role": "member" }, { "email": "tfm@caltech.edu", "id": "Miller-T-F", "name": { "family": "Miller", "given": "Thomas F." }, "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_defense_date": "2019-05-06", "gradofc_approval_date": "2019-05-31", "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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21:38:31", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "tratani@gmail.com", "id": "Ratani-Tanvi-Siraj", "name": { "family": "Ratani", "given": "Tanvi Siraj" }, "show_email": "NO" } ] }, "title": "Photoinduced, Copper-Catalyzed C-N and C-C Bond Formation and Photocatalytic Co-Mediated Nitrite Reduction to N\u2082O: Reactivity and Mechanism", "ispublished": "unpub", "full_text_status": "public", "keywords": "photocatalysis, photoredox catalysis, copper catalysis, cross-coupling, nitrite reduction", "abstract": "Photocatalytic reactions with first-row transition metals are presented as a method for sustainable chemistry with great potential for new forms of reactivity and mechanistic pathways. Chapters 2 and 3 of this thesis discuss mechanism and reactivity of photoinduced, copper-catalyzed bond constructions. The Peters and Fu groups have reported that a variety of couplings of nitrogen, sulfur, oxygen, and carbon nucleophiles with organic halides can be achieved under mild conditions (\u221240 to 30 \u00b0C) through the use of light and a copper catalyst. Insight into the various mechanisms by which these reactions proceed may enhance our understanding of chemical reactivity and facilitate the development of new methods. We apply an array of tools (EPR, NMR, transient absorption, and UV\u2212vis spectroscopy; ESI\u2212MS; X-ray crystallography; DFT calculations; reactivity, stereochemical, and product studies) to investigate the photoinduced, copper-catalyzed coupling of carbazole with alkyl bromides. Our observations are consistent with pathways wherein both an excited state of the copper(I) carbazolide complex ([CuI(carb)2]\u2212) and an excited state of the nucleophile (Li(carb)) can serve as photoreductants of the alkyl bromide. The catalytically dominant pathway proceeds from the excited state of Li(carb), generating a carbazyl radical and an alkyl radical. The cross-coupling of these radicals is catalyzed by copper via an out-of-cage mechanism in which [CuI(carb)2]\u2212 and [CuII(carb)3]\u2212 (carb = carbazolide), both of which have been identified under coupling conditions, are key intermediates, and [CuII(carb)3]\u2212 serves as the persistent radical that is responsible for predominant cross-coupling. This study underscores the versatility of copper(II) complexes in engaging with radical intermediates that are generated by disparate pathways, en route to targeted bond constructions.
\r\n\r\nIn Chapter 3, we establish that photoinduced, copper-catalyzed alkylation can also be applied to C\u2212C bond formation, specifically, that the cyanation of unactivated secondary alkyl chlorides can be achieved at room temperature to afford nitriles, an important class of target molecules. In the presence of an inexpensive copper catalyst (CuI; no ligand coadditive) and a readily available light source (UVC compact fluorescent light bulb), a wide array of alkyl halides undergo cyanation in good yield. Our initial mechanistic studies are consistent with the hypothesis that an excited state of [Cu(CN)2]\u2212 may play a role, via single electron transfer, in this process. This investigation provides a rare example of a transition metal-catalyzed cyanation of an alkyl halide, as well as the first illustrations of photoinduced, copper-catalyzed alkylation with either a carbon nucleophile or a secondary alkyl chloride.
\r\n\r\nChapter 4 presents a mechanistic study of the photocatalytic reduction of nitrite to nitrous oxide with the use of an Ir photocatalyst ([Ir(ppy)2(phen)][PF6]) and a bimetallic CoMg co-catalyst with a diimine-dioxime ligand platform. Insights into the mechanism of this reaction may enhance our current understanding of N\u2013N coupling processes relative to other pathways of reactivity for nitrosyl ligands, such as nitroxyl (HNO) dimerization. We propose a mechanism in which a coordinated and an uncoordinated \u2022NO are coupled at a single Co center. One electron reduction of [(Cl)(NO)Co(Medoen)Mg(Me3TACN)(H2O)][BPh4] ({CoNO}8), a species we show to be catalytically relevant, forms a {CoNO}9 species that is characterized by UV-Vis, EPR, and FT-IR spectroscopy and whose electronic structure is supported by density functional theory (DFT). We formulate the {CoNO}9 as a 5-coordinate, S = 3/2 Co(II) antiferromagnetically coupled with an anionic S = 1 3NO\u2013 ligand. Experimental data suggest a mechanism in which this {CoNO}9 intermediate can release \u2022NO, thereby reducing the Co(II) center to Co(I). This free \u2022NO can react with another {CoNO}9 complex to generate a Co(NONO) intermediate which was observed by step-scan time-resolved IR spectroscopy and whose assignment was supported with DFT calculations. This Co(NONO) species, which can generate N2O and H2O, is formulated as a neutral hyponitrite intermediate with significant neutral radical character on both nitrosyl nitrogen atoms and a weak N\u2013N bond.
", "date": "2018", "date_type": "degree", "id_number": "CaltechTHESIS:10312017-153922571", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:10312017-153922571", "related_url": { "items": [ { "description": "Article adapted for Ch. 2.", "type": "doi", "url": "http://dx.doi.org/10.1021/jacs.7b07052" }, { "description": "Article adapted for Ch. 3.", "type": "doi", "url": "http://dx.doi.org/10.1021/jacs.5b08452" } ] }, "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "National Science Foundation Graduate Research Fellowship" } ] }, "collection": "CaltechTHESIS", "reviewer": "Melissa Ray", "suggestions": "Released to public view 1/23/2019 // Extension approved till 11/1/2018 // Extension requested 04132018. Being routed through committee. Expiry date provisionally extended // Restricted to Caltech community only until 1 May 2018. // From author: Chapter 4 and Appendix C in this thesis will be published after my graduation, potentially in an ACS journal.", "deposited_by": "Tanvi Ratani", "deposited_on": "2017-12-27 21:38:31", "doi": "10.7907/Z9ZP44BF", "alt_title": { "items": [ "Photoinduced, Copper-catalyzed C-N and C-C Bond Formation and Photocatalytic Co-mediated Nitrite Reduction to N_2O: Reactivity and Mechanism", "Photoinduced, Copper-Catalyzed C-N and C-C Bond Formation and Photocatalytic Co-Mediated Nitrite Reduction to N2O: Reactivity and Mechanism" ] }, "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "jpeters@caltech.edu", "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "agapie@caltech.edu", "id": "Agapie-T", "name": { "family": "Agapie", "given": "Theodor" }, "role": "chair" }, { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "member" }, { "email": "gcfu@caltech.edu", "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "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_defense_date": "2017-10-30", "gradofc_approval_date": "2017-12-22", "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": "2018", "author_list": "Ratani, Tanvi Siraj", "advisor_list": "Peters, Jonas C.", "comittee_list": "Agapie, Theodor; Gray, Harry B.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/10956", "eprint_id": 10956, "rev_number": 64, "documents": [ { "id": "/id/document/90397", "doc_id": 90397, "rev_number": 5, "files": [ { "id": "/id/file/255493", "fileid": 255493, "datasetid": "document", "objectid": 90397, "filename": "Ahn, JM Caltech Thesis.docx", "mime_type": "application/vnd.openxmlformats-officedocument.wordprocessingml.document", "hash": "c3879c552269ba692b13459af5d52277", "hash_type": "MD5", "filesize": 13754255, "mtime": "2018-05-29 23:39:10", "url": "/10956/7/Ahn, JM Caltech Thesis.docx" } ], "eprint_id": 10956, "pos": 7, "placement": 3, "mime_type": 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conversion from application/pdf 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/95113" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/95113" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/95113" } ] } } ], "eprint_status": "archive", "userid": 11617, "dir": "disk0/00/01/09/56", "datestamp": "2018-05-30 18:38:20", "lastmod": "2023-11-08 00:44:05", "status_changed": "2018-05-30 18:38:20", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "joe.jm.ahn@gmail.com", "id": "Ahn-Jun-Myun", "name": { "family": "Ahn", "given": "Jun Myun" }, "orcid": "0000-0002-8181-908X", "show_email": "NO" } ] }, "title": "Copper Carbazolides in Photoinduced C\u2013N Couplings", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry; copper; spectroscopy; reactivity studies; mechanistic studies; cross-coupling; photochemistry; ", "abstract": "Photoinduced, copper-catalyzed reactions of organohalides have emerged in recent years as a powerful tool to construct a wide array of C\u2013N bonds, which are prevalent in organic materials and polymers, pharmaceuticals, natural products, and ligands in transition metal catalysts. Described herein is the study and applications of copper complexes ligated by carbazole and its derivatives in photoinduced, copper-catalyzed C\u2013N bond-constructing transformations. Various areas of synthetic inorganic and organic chemistry are explored, including in-depth mechanistic elucidation, ligand and catalyst design, reaction development, as well as spectroscopic and structural characterization of reactive copper complexes.\r\nChapter 2 describes the mechanistic investigation on photoinduced, copper-catalyzed couplings of carbazoles with unactivated alkyl halides. A wide array of mechanistic tools suggests the viability of an out-of-cage C(sp\u00b3)\u2013N coupling pathway. Spectroscopic and structural characterization data of the key intermediates are detailed.\r\nChapter 3 outlines the design and preparation of a new copper-based photoredox catalyst supported by a tridentate bis(phosphino)carbazole ligands. The ground- and excited-state properties of the new photocatalyst are examined.\r\nChapter 4 details the development of photoinduced, copper-catalyzed C(sp\u00b3)\u2013N couplings of carbamates with unactivated alkyl bromides using the new copper photoredox system. The scope with respect to the nucleophile and the electrophile and mechanistic investigations are communicated.\r\nChapter 5 illustrates the chemistry of copper complexes supported by bidentate (phosphino)carbazole ligands. A diverse array of copper complexes in both the S = 0 and S = 1/2 states are reported, including a rare, paramagnetic copper\u2013phosphine complex that may serve as a structural model for key copper intermediates of the enantioselective C(sp\u00b3)\u2013N couplings of carbazoles.", "date": "2018", "date_type": "degree", "id_number": "CaltechTHESIS:05282018-184138570", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:05282018-184138570", "related_url": { "items": [ { "description": "Article adapted for ch. 2", "type": "doi", "url": "https:/doi.org/10.1021/jacs.7b07052" }, { "description": "Article adapted ch. 3-4", "type": "doi", "url": "https:/doi.org/10.1021/jacs.7b10907" } ] }, "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "deposited_by": "Jun Myun Ahn", "deposited_on": "2018-05-30 18:38:20", "doi": "10.7907/H8AP-G249", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "gcfu@caltech.edu", "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "role": "co-advisor" }, { "email": "jpeters@caltech.edu", "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "role": "co-advisor" } ] }, "thesis_committee": { "items": [ { "email": "agapie@caltech.edu", "id": "Agapie-T", "name": { "family": "Agapie", "given": "Theodor" }, "role": "chair" }, { "email": "gcfu@caltech.edu", "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "role": "member" }, { "email": "jpeters@caltech.edu", "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "role": "member" }, { "email": "reisman@caltech.edu", "id": "Reisman-S-E", "name": { "family": "Reisman", "given": "Sarah E." }, "role": "member" }, { "email": "stoltz@caltech.edu", "id": "Stoltz-B-M", "name": { "family": "Stoltz", "given": "Brian M." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "2018-05-18", "gradofc_approval_date": "2018-05-30", "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": "2018", "author_list": "Ahn, Jun Myun", "advisor_list": "Fu, Gregory C. and Peters, Jonas C.", "comittee_list": "Agapie, Theodor; Fu, Gregory C.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/10443", "eprint_id": 10443, "rev_number": 31, "documents": [ { "id": "/id/document/82729", "doc_id": 82729, "rev_number": 4, "files": [ { "id": "/id/file/233934", "fileid": 233934, "datasetid": "document", "objectid": 82729, "filename": "Buscagan_Trixia_2018_Thesis.pdf", "mime_type": "application/pdf", "hash": "fe57b5079b7c6d6e68949e86d22a08ef", "hash_type": "MD5", "filesize": 8885097, "mtime": "2017-09-21 15:19:52", "url": "/10443/1/Buscagan_Trixia_2018_Thesis.pdf" } ], "eprint_id": 10443, "pos": 1, "placement": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": 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"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/82729" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/82729" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/82729" } ] } } ], "eprint_status": "archive", "userid": 11354, "dir": "disk0/00/01/04/43", "datestamp": "2017-09-25 22:47:56", "lastmod": "2023-11-08 00:44:05", "status_changed": "2017-09-25 22:47:56", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "trixia.marie.b@gmail.com", "id": "Buscagan-Trixia-Marie", "name": { "family": "Buscagan", "given": "Trixia Marie" }, "orcid": "0000-0001-8242-9203", "show_email": "NO" } ] }, "title": "Transition Metals as Catalysts for Cross-Coupling and Dinitrogen Fixation", "ispublished": "unpub", "full_text_status": "public", "keywords": "transition metal, catalysis, dinitrogen reduction, cross coupling, iron catalyst, nickel catalyst", "abstract": "Transition metals are used as catalysts in the laboratory and by nature to facilitate difficult chemical transformations. Herein, three different metal containing catalysts are discussed: Pd and Ni catalysts towards the formation of carbon-carbon (C-C) bonds and Fe catalysts towards the reduction of N2 to NH3.
\r\n\r\nIn Chapter 2, mechanistic studies of Pd- and Ni-catalyzed cross-coupling reactions are discussed. The mechanism of transmetalation of a Pd-catalyzed Suzuki cross-coupling reaction is studied using a stereochemical probe, revealing that transmetalation occurs with retention of configuration, consistent with transmetalation occurring through a frontside-attack mechanism. Next, to explore the viability of a transmetalation first pathway in an asymmetric Negishi cross-coupling reaction, S = 1/2 NiIBr and NiI\u2013alkyl complexes were synthesized, crystallographically characterized, and their reactivities explored. Based on these reactivity studies, evidence against a transmetalation first pathway is provided using a variety of spectroscopic methods.
\r\n\r\nIn Chapter 3, new Fe(N2)(H)x complexes are synthesized. These complexes catalyze the reduction of N2 to NH3 and the yields for NH3 are improved if the reactions are performed in the presence of Hg lamp photolysis. Preliminary mechanistic studies exploring the role of light are discussed. In the final chapter, new ligand scaffolds are developed that can bind a Lewis acidic and Lewis basic metal center. These ligand frameworks support one- and two-atom bridges between the two metal sites. Finally, we discovered that some of the new complexes are catalysts for N2 to NH3 reduction and olefin hydrogenation.
", "date": "2018", "date_type": "degree", "id_number": "CaltechTHESIS:09202017-130540216", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:09202017-130540216", "related_url": { "items": [ { "description": "Article adapted for Chapter 3.", "type": "doi", "url": "http://dx.doi.org/10.1002/anie.201703244" } ] }, "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Melissa Ray", "deposited_by": "Trixia Buscagan", "deposited_on": "2017-09-25 22:47:56", "doi": "10.7907/Z98P5XPM", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "jpeters@caltech.edu", "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "reisman@caltech.edu", "id": "Reisman-S-E", "name": { "family": "Reisman", "given": "Sarah E." }, "role": "chair" }, { "email": "gcfu@caltech.edu", "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "role": "member" }, { "email": "agapie@caltech.edu", "id": "Agapie-T", "name": { "family": "Agapie", "given": "Theodor" }, "role": "member" }, { "email": "dcrees@caltech.edu", "id": "Rees-D-C", "name": { "family": "Rees", "given": "Douglas C." }, "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_defense_date": "2017-08-28", "gradofc_approval_date": "2107-09-25", "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": "2018", "author_list": "Buscagan, Trixia Marie", "advisor_list": "Peters, Jonas C.", "comittee_list": "Reisman, Sarah E.; Fu, Gregory C.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/10732", "eprint_id": 10732, "rev_number": 51, "documents": [ { "id": "/id/document/86702", "doc_id": 86702, "rev_number": 5, "files": [ { "id": "/id/file/245714", "fileid": 245714, "datasetid": "document", "objectid": 86702, "filename": "nesbit-mark-6-month-embargo-request.pdf", "mime_type": "application/pdf", "hash": "9994e1015dd490953bc7d55124c24f18", "hash_type": "MD5", "filesize": 59734, "mtime": "2018-02-26 18:30:07", "url": "/10732/7/nesbit-mark-6-month-embargo-request.pdf" } ], "eprint_id": 10732, "pos": 7, "placement": 3, "mime_type": "application/pdf", "format": "application/pdf", "format_desc": "Author 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"format_desc": "Generate index codes conversion from application/pdf 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/102039" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/102039" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/102039" } ] } } ], "eprint_status": "archive", "userid": 11465, "dir": "disk0/00/01/07/32", "datestamp": "2018-03-13 17:02:47", "lastmod": "2023-11-08 00:44:05", "status_changed": "2018-03-13 17:02:47", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "mnesbit313@gmail.com", "id": "Nesbit-Mark-Allen", "name": { "family": "Nesbit", "given": "Mark Allen" }, "orcid": "0000-0002-5642-9303", "show_email": "NO" } ] }, "title": "Iron, Cobalt, and Nickel Metalloboranes: Reactivity, Catalysis, N2 Activation and Stabilization of Reactive N2Hx Ligands", "ispublished": "unpub", "full_text_status": "public", "keywords": "Small Molecule Activation; Transition Metal Catalysis; Metalloboranes; Nitrogen Fixation", "abstract": "The reactivity of Fe and Co compounds supported by a bisphosphinoborane (DPB) ligand ([(DPB)Fe]2(N2) and (DPB)Co(N2)) towards E-H bonds (E = C, N, S, O, Si) is reported along with the catalytic hydrosilylation of ketones and aldehydes. The Fe and Co compounds displayed a mix of 1-electron and 2-electron chemistry. In some cases [(DPB)Fe]2(N2) and (DPB)Co(N2) facilitated oxidative addition of the E-H bond across the M-B interaction, and in others evolution of H2 giving a 1-electron oxidized complex of the general form (DPB)M(E) was observed. The reaction of Ph2SiH2 with (DPB)Co(N2) was found to be reversible, similar to the previously reported related nickel complex (PhDPBMes)Ni. The reactivity of these Fe and Co compounds is compared to previously reported Ni compounds supported by a similar ligand which catalyze olefin hydrogenation and hydrosilylation of substituted benzaldehydes.
\r\n\r\nThe synthesis and metalation with nickel of two new variants of the DPB ligand (DP*BPh and DP*BMes) is described. The primary modification introduced in DP*BPh and DP*BMes is the incorporation of a tertiary amine moiety into the secondary coordination sphere. This was done with the hypothesis that the amine moiety might act as a proton shuttle and facilitate proton reduction or hydrogen oxidation electrocatalysis. The process of screening these compounds for activity as proton reduction and hydrogen oxidation catalysts is also discussed. Additionally, the stoichiometric reactivity of [(DP*BPh)Ni]2(N2) and (DP*BMes)Ni(N2) with H2 was studied. We observed that [(DP*BPh)Ni]2(N2) slowly decomposed to an unidentified mixture of products while (DP*BMes)Ni(N2) dimerized to form a phosphine bridged Ni-borohydride dimer [(DP*BMesH)Ni]2. [(DP*BPh)Ni]2(N2) and (DP*BMes)Ni(N2) were also tested as precatalysts for olefin hydrogenation and found to be less active that their previously reported counterpart (PhDPBMes)Ni. [(DP*BPh)Ni]2(N2) and (DP*BMes)Ni(N2) correspondingly showed no activity for hydrogenation of polar substrates such as ketones, aldehydes, or CO2.
\r\n\r\nLastly, the synthesis of a new trisphosphinoborane ligand (ArP3B) with bulky aryl substituents on the phosphines and its metalation with Fe is described. The anionic-N2 adduct [(ArP3B)Fe(N2)][Na(12-C-4)2] was observed to react with H+ sources to generate the first observed parent iron-diazenido (ArP3B)Fe(NNH) and an iron-hydrazido(2-) [(ArP3B)Fe(NNH2)]+. [(ArP3B)Fe(NNH2)]+ was found to have similar spectroscopic properties to the previously reported [(TPB)Fe(NNH2)]+. A thorough characterization of [(ArP3B)Fe(N2)][Na(12-C-4)2], (ArP3B)Fe(NNH), and [(ArP3B)Fe(NNH2)]+ by a variety of continuous wave and pulsed ERP techniques is presented along with 57Fe M\u00f6ssbauer data. The new (ArP3B)Fe system was also canvassed for activity as a catalyst for conversion of N2 to NH3 and found to yield substoichiometric amounts of NH3 in the presence of KC8 and HBArF24\u20222Et2O while no NH3 was observed using CoCp*2 and [H2NPh2][OTf].
", "date": "2018", "date_type": "degree", "id_number": "CaltechTHESIS:02232018-173939270", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:02232018-173939270", "related_url": { "items": [ { "description": "Article adapted for Ch. 2.", "type": "doi", "url": "https://doi.org/10.1021/acs.organomet.5b00530" } ] }, "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Melissa Ray", "suggestions": "Released to public view 25 June 2019. //\r\nRestricted to campus only. 1 extension request 13 August 2018.", "deposited_by": "Mark Nesbit", "deposited_on": "2018-03-13 17:02:47", "doi": "10.7907/Z9G15Z28", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "jpeters@caltech.edu", "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "jkbarton@caltech.edu", "id": "Barton-J-K", "name": { "family": "Barton", "given": "Jacqueline K." }, "role": "chair" }, { "email": "gcfu@caltech.edu", "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "role": "member" }, { "email": "agapie@caltech.edi", "id": "Agapie-T", "name": { "family": "Agapie", "given": "Theodor" }, "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_defense_date": "2018-01-08", "gradofc_approval_date": "2018-03-12", "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": "2018", "author_list": "Nesbit, Mark Allen", "advisor_list": "Peters, Jonas C.", "comittee_list": "Barton, Jacqueline K.; Fu, Gregory C.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/10965", "eprint_id": 10965, "rev_number": 53, "documents": [ { "id": "/id/document/91033", "doc_id": 91033, "rev_number": 7, "files": [ { "id": "/id/file/256950", "fileid": 256950, "datasetid": "document", "objectid": 91033, "filename": "thompson_niklas_2018.tex", "mime_type": "text/plain", "hash": "0a72dcee2751db5ed8582ac24a76b46c", "hash_type": "MD5", "filesize": 787785, "mtime": "2018-06-01 02:09:20", "url": "/10965/7/thompson_niklas_2018.tex" } ], "eprint_id": 10965, "pos": 7, "placement": 5, "mime_type": "text/plain", "format": "application/x-latex", "format_desc": "Source Code", "language": "en", 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"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/104331" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/104331" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/104331" } ] } } ], "eprint_status": "archive", "userid": 10771, "dir": "disk0/00/01/09/65", "datestamp": "2018-06-01 18:51:40", "lastmod": "2023-11-08 00:44:05", "status_changed": "2018-06-01 18:51:40", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "niklas.b.t@gmail.com", "id": "Thompson-Niklas-Bjarne", "name": { "family": "Thompson", "given": "Niklas Bjarne" }, "orcid": "0000-0003-2745-4945", "show_email": "NO" } ] }, "title": "A Synthetic Nitrogenase: Insights into the Mechanism of Nitrogen Fixation by a Single-Site Fe Catalyst", "ispublished": "unpub", "full_text_status": "public", "keywords": "Nitrogen fixation; ammonia synthesis; Fe catalysis", "abstract": "Nitrogen fixation, specifically the conversion of molecular nitrogen into ammonia, is a fundamental reaction necessary to support life. Our group has recently discovered the first family of well-defined iron complexes that catalyze the conversion of dinitrogen to ammonia. This thesis details mechanistic study of the nitrogen fixation chemistry these complexes. Chapter 1 presents an abbreviated overview of catalytic nitrogen fixation, which places our work in a larger context. Chapter 2 details the synthesis and nitrogen fixation activity of a series of cobalt complexes that are homologous to the known iron-based catalysts. The central goal of this work was to provide a structure-function study of the isostructural cobalt and iron complexes, in which the nature of the transition metal ion was changed in a fashion that predictably modulated the electronics of the system. Chapter 3 details in situ mechanistic studies of nitrogen fixation catalyzed by the iron complexes under the originally-reported reaction conditions. In this study, we were able to achieve a nearly order-of-magnitude improvement of catalyst turnover. Study of the reaction dynamics evidence a single-site mechanism for dinitrogen reduction, which is corroborated by in situ monitoring of catalytic reaction mixtures using freeze-quench M\u00f6ssbauer spectroscopy. In Chapter 4, we study the key N-N bond cleavage step in the catalytic cycle for nitrogen fixation. In this chapter, we demonstrate that sequential reduction and low-temperature protonation of an iron catalyst results in the formation of ammonia and a terminal Fe(IV) nitrido complex. This result provides a compelling proposal for the mechanism of the catalytic nitrogen fixation reaction. Finally, in Chapter 5 we present spectroscopic and computational studies detailing the electronic structures of a redox series of Fe(NNR2) complexes that model key catalytic intermediates occurring prior to the N-N bond cleavage step. We evidence one-electron redox non-innocence of the \u201cNNR2\u201d ligand, which resembles that of the classically non-innocent ligand, NO, and may have mechanistic implications for the divergent nitrogen fixation activity of the some of the iron complexes studied by our group.
", "date": "2018", "date_type": "degree", "id_number": "CaltechTHESIS:05292018-165300346", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:05292018-165300346", "related_url": { "items": [ { "description": "Published content for Chapter 2.", "type": "doi", "url": "https://doi.org/10.1021/acs.inorgchem.5b00645" }, { "description": "Published content for Chapter 3.", "type": "doi", "url": "https://doi.org/10.1021/jacs.6b01706" }, { "description": "Published content for Chapter 4.", "type": "doi", "url": "https://doi.org/10.1021/jacs.7b09364" } ] }, "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "GM 070757" } ] }, "collection": "CaltechTHESIS", "reviewer": "Melissa Ray", "local_group": { "items": [ "Resnick Sustainability Institute" ] }, "suggestions": "Released to public 4 December 2019. //\r\n\r\nSecond embargo extension request approved 2019-06-24 // Restricted to Caltech community only until 3 December 2019 // From author: The thesis includes portions that are being considered for publication in an ACS journal (Inorganic Chemistry). \r\n\r\n// Embargo extension request approved 2018-11-09 // Restricted to Caltech community only until 3 June 2019 // From author: We request an embargo as unpublished content of this thesis is under review for publication by the American Chemical Society. \r\n\r\n// Original embargo request // Restricted to Caltech community only until 3 December 2018. // From author: We request an embargo as unpublished content of this thesis is under review.", "deposited_by": "Niklas Thompson", "deposited_on": "2018-06-01 18:51:40", "doi": "10.7907/T4WQ-TM68", "alt_title": { "items": [ "Insights into the Mechanism of Nitrogen Fixation by a Single-Site Fe Catalyst" ] }, "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "jpeters@caltech.edu", "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "agapie@caltech.edu", "id": "Agapie-T", "name": { "family": "Agapie", "given": "Theodor" }, "role": "chair" }, { "email": "gcfu@caltech.edu", "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "role": "member" }, { "email": "gkc1000@gmail.com", "id": "Chan-G-K", "name": { "family": "Chan", "given": "Garnet K." }, "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_defense_date": "2018-05-25", "gradofc_approval_date": "2018-06-01", "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": "2018", "author_list": "Thompson, Niklas Bjarne", "advisor_list": "Peters, Jonas C.", "comittee_list": "Agapie, Theodor; Fu, Gregory C.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/10893", "eprint_id": 10893, "rev_number": 147, "documents": [ { "id": "/id/document/88725", "doc_id": 88725, "rev_number": 7, "files": [ { "id": "/id/file/251743", "fileid": 251743, "datasetid": "document", "objectid": 88725, "filename": "Chapter 1_mjc_edit.pdf", "mime_type": "application/pdf", "hash": "01541c78e0656c353c3248686027060e", "hash_type": "MD5", "filesize": 208186, "mtime": "2018-05-15 22:56:53", "url": "/10893/15/Chapter 1_mjc_edit.pdf" } ], "eprint_id": 10893, "pos": 15, "placement": 2, "mime_type": "application/pdf", "format": "application/pdf", "format_desc": "Chapter 1", "language": "en", 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21:18:42", "lastmod": "2023-11-08 00:44:05", "status_changed": "2018-05-22 21:18:42", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "tjdelcastillo@gmail.com", "id": "Del-Castillo-Trevor-James", "name": { "family": "Del Castillo", "given": "Trevor James" }, "orcid": "0000-0001-5120-1935", "show_email": "NO" } ] }, "title": "The Quest for Electrocatalytic Nitrogen Fixation with a Molecular Catalyst and What We Learned Along the Way", "ispublished": "unpub", "full_text_status": "public", "keywords": "Nitrogen fixation, electrochemistry, electrocatalysis", "abstract": "This report details research into the mechanism and operating principles underlying the nitrogen fixation efficacy of a tris(phosphine)borane iron complex (P3BFe). The data presented provide what is to our knowledge the first unambiguous demonstration of electrocatalytic nitrogen fixation by a molecular catalyst and contribute to a growing body of evidence that metallocenes may play multiple roles during reductive catalysis.
", "date": "2018", "date_type": "degree", "id_number": "CaltechTHESIS:05152018-150143251", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:05152018-150143251", "related_url": { "items": [ { "description": "Article adapted for Chapter 2.", "type": "doi", "url": "https://doi.org/10.1021/acs.inorgchem.5b00645" }, { "description": "Article adapted for Chapter 3.", "type": "doi", "url": "https://doi.org/10.1021/jacs.6b01706" }, { "description": "Article adapted for Chapter 4.", "type": "doi", "url": "https://doi.org/10.1021/acscentsci.7b00014" }, { "description": "Article adapted for Chapter 5", "type": "doi", "url": "https://doi.org/10.1021/jacs.8b02335" } ] }, "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Melissa Ray", "deposited_by": "Trevor Del Castillo", "deposited_on": "2018-05-22 21:18:42", "doi": "10.7907/CM5B-RG20", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "jpeters@caltech.edu", "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "jkbarton@caltech.edu", "id": "Barton-J-K", "name": { "family": "Barton", "given": "Jacqueline K." }, "role": "chair" }, { "email": "dadoc@caltech.edu", "id": "Dougherty-D-A", "name": { "family": "Dougherty", "given": "Dennis A." }, "role": "member" }, { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "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_defense_date": "2018-04-23", "gradofc_approval_date": "2018-05-22", "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": "2018", "author_list": "Del Castillo, Trevor James", "advisor_list": "Peters, Jonas C.", "comittee_list": "Barton, Jacqueline K.; Dougherty, Dennis A.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/10731", "eprint_id": 10731, "rev_number": 90, "documents": [ { "id": "/id/document/86696", "doc_id": 86696, "rev_number": 3, "files": [ { "id": "/id/file/245700", "fileid": 245700, "datasetid": "document", "objectid": 86696, "filename": "matson-benjamin-6-month-embargo-request.pdf", "mime_type": "application/pdf", "hash": "ec922e3c3323bd9e79b0d12a84e56caa", "hash_type": "MD5", "filesize": 59403, "mtime": "2018-02-26 17:54:29", "url": "/10731/7/matson-benjamin-6-month-embargo-request.pdf" } ], "eprint_id": 10731, "pos": 7, "placement": 7, "mime_type": "application/pdf", "format": "application/pdf", 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"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/86714" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/86714" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/86714" } ] } } ], "eprint_status": "archive", "userid": 10787, "dir": "disk0/00/01/07/31", "datestamp": "2018-03-09 17:27:48", "lastmod": "2023-11-08 00:44:05", "status_changed": "2018-03-09 17:27:48", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "bdmatson@gmail.com", "id": "Matson-Benjamin-David", "name": { "family": "Matson", "given": "Benjamin David" }, "orcid": "0000-0001-5733-0893", "show_email": "YES" } ] }, "title": "Interplay of Proton Transfer, Electron Transfer and Proton-Coupled Electron Transfer in Transition Metal Mediated Nitrogen Fixation", "ispublished": "unpub", "full_text_status": "public", "keywords": "Inorganic Chemistry; Theoretical Chemistry; Computational Chemistry", "abstract": "Mitigation of the hydrogen evolution reaction (HER) is a key challenge in selective small molecule reduction catalysis, including the nitrogen (N2) reduction reactions (N2RR) using H+/e- currency. Here we explore, via DFT calculations, three iron model systems, P3EFe (E = B, Si, C), known to mediate both N2RR and HER, but with different selectivity depending on the identity of the auxiliary ligand. It is shown that the respective efficiencies of these systems for N2RR trend with the predicted N\u2013H bonds strengths of two putative hydrazido intermediates of the proposed catalytic cycle, P3EFe(NNH2)+ and P3EFe(NNH2). Bimolecular proton-coupled electron transfer (PCET) from intermediates with weak N\u2013H bonds is posited as a major source of H2 instead of more traditional scenarios that proceed via metal hydride intermediates and proton transfer/electron transfer (PT/ET) pathways.
\r\n\r\nStudies on our most efficient molecular iron catalyst, [P3BFe]+, reveal that the interaction of acid and reductant, Cp*2Co, is critical to achieve high efficiency for NH3, leading to the demonstration of electrocatalytic N2RR. Stoichiometric reactivity shows that Cp*2Co is required to observe productive N\u2013H bond formation with anilinium triflate acids under catalytic conditions. A study of substituted anilinium triflate acids demonstrates a strong correlation between pKa and the efficiency for NH3, which DFT studies attribute to the kinetics and thermodynamics of Cp*2Co protonation. These results contribute to the growing body of evidence suggesting that metallocenes should be considered as more than single electron transfer reagents in the proton-coupled reduction of small molecule substrates and that ring-functionalized metallocenes, believed to be intermediates on the background HER pathway, can play a critical role in productive bond-forming steps.
", "date": "2018", "date_type": "degree", "id_number": "CaltechTHESIS:02232018-152758526", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:02232018-152758526", "related_url": { "items": [ { "description": "Chapter 1 -- published material.", "type": "doi", "url": "http://dx.doi.org/10.1021/acscatal.7b03068" }, { "description": "Chapter 2 -- published material.", "type": "doi", "url": "http://dx.doi.org/10.1021/acscentsci.7b00014" } ] }, "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Melissa Ray", "local_group": { "items": [ "Resnick Sustainability Institute" ] }, "deposited_by": "Benjamin Matson", "deposited_on": "2018-03-09 17:27:48", "doi": "10.7907/Z9MS3R0Z", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "jpeters@caltech.edu", "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "agapie@caltech.edu", "id": "Agapie-T", "name": { "family": "Agapie", "given": "Theodor" }, "role": "chair" }, { "email": "tfm@caltech.edu", "id": "Miller-T-F", "name": { "family": "Miller", "given": "Thomas F." }, "role": "member" }, { "email": "lhw@caltech.edu", "id": "Hsieh-Wilson-L-C", "name": { "family": "Hsieh-Wilson", "given": "Linda C." }, "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_defense_date": "2018-02-09", "gradofc_approval_date": "2018-03-08", "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": "2018", "author_list": "Matson, Benjamin David", "advisor_list": "Peters, Jonas C.", "comittee_list": "Agapie, Theodor; Miller, Thomas F.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/9581", "eprint_id": 9581, "rev_number": 27, "documents": [ { "id": "/id/document/63876", "doc_id": 63876, "rev_number": 4, "files": [ { "id": "/id/file/178950", "fileid": 178950, "datasetid": "document", "objectid": 63876, "filename": "creutz_thesis.pdf", "mime_type": "application/pdf", "hash": "4e73dc8f87f0763b89206ae1e5913f0f", "hash_type": "MD5", "filesize": 14691473, "mtime": "2016-02-24 21:23:08", "url": "/9581/1/creutz_thesis.pdf" } ], "eprint_id": 9581, "pos": 1, "placement": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": 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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/63876" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/63876" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/63876" } ] } } ], "eprint_status": "archive", "userid": 3362, "dir": "disk0/00/00/95/81", "datestamp": "2016-03-01 22:58:17", "lastmod": "2023-11-08 00:44:05", "status_changed": "2016-03-01 22:58:17", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "secreutz@gmail.com", "id": "Creutz-Sidney-E", "name": { "family": "Creutz", "given": "Sidney E." }, "show_email": "YES" } ] }, "title": "Design, Synthesis, and Study of Novel Platforms for Iron-N2 Chemistry and Photoinduced, Copper-mediated C-N Bond Formation", "ispublished": "unpub", "full_text_status": "public", "keywords": "nitrogen activation, catalysis, iron phosphine complexes, copper coupling, photoinduced coupling, nitrogenase modeling ", "abstract": "Several new ligand platforms designed to support iron dinitrogen chemistry have been developed. First, we report Fe complexes of a tris(phosphino)alkyl (CPiPr3) ligand featuring an axial carbon donor intended to conceptually model the interstitial carbide atom of the nitrogenase iron-molybdenum cofactor (FeMoco). It is established that in this scaffold, the iron center binds dinitrogen trans to the Calkyl anchor in three structurally characterized oxidation states. Fe-Calkyl lengthening is observed upon reduction, reflective of significant ionic character in the Fe-Calkyl interaction. The anionic (CPiPr3)FeN2- species can be functionalized by a silyl electrophile to generate (CPiPr3)Fe-N2SiR3. This species also functions as a modest catalyst for the reduction of N2 to NH3. Next, we introduce a new binucleating ligand scaffold that supports an Fe(\u03bc-SAr)Fe diiron subunit that coordinates dinitrogen (N2-Fe(\u03bc-SAr)Fe-N2) across at least three oxidation states (FeIIFeII, FeIIFeI, and FeIFeI). Despite the sulfur-rich coordination environment of iron in FeMoco, synthetic examples of transition metal model complexes that bind N2 and also feature sulfur donor ligands remain scarce; these complexes thus represent an unusual series of low-valent diiron complexes featuring thiolate and dinitrogen ligands. The (N2-Fe(\u03bc-SAr)Fe-N2) system undergoes reduction of the bound N2 to produce NH3 (~50% yield) and can efficiently catalyze the disproportionation of N2H4 to NH3 and N2. The present scaffold also supports dinitrogen binding concomitant with hydride as a co-ligand. Next, inspired by the importance of secondary-sphere interactions in many metalloenzymes, we present complexes of iron in two new ligand scaffolds ([SiPNMe3] and [SiPiPr2PNMe]) that incorporate hydrogen-bond acceptors (tertiary amines) which engage in interactions with nitrogenous substrates bound to the iron center (NH3 and N2H4). Cation binding is also facilitated in anionic Fe(0)-N2 complexes. While Fe-N2 complexes of a related ligand ([SiPiPr3]) lacking hydrogen-bond acceptors produce a substantial amount of ammonia when treated with acid and reductant, the presence of the pendant amines instead facilitates the formation of metal hydride species.
\r\n\r\nAdditionally, we present the development and mechanistic study of copper-mediated and copper-catalyzed photoinduced C-N bond forming reactions. Irradiation of a copper-amido complex, ((m-tol)3P)2Cu(carbazolide), in the presence of aryl halides furnishes N-phenylcarbazole under mild conditions. The mechanism likely proceeds via single-electron transfer from an excited state of the copper complex to the aryl halide, generating an aryl radical. An array of experimental data are consistent with a radical intermediate, including a cyclization/stereochemical investigation and a reactivity study, providing the first substantial experimental support for the viability of a radical pathway for Ullmann C-N bond formation. The copper complex can also be used as a precatalyst for Ullmann C-N couplings. We also disclose further study of catalytic Calkyl-N couplings using a CuI precatalyst, and discuss the likely role of [Cu(carbazolide)2]- and [Cu(carbazolide)3]- species as intermediates in these reactions.
\r\n \r\nFinally, we report a series of four-coordinate, pseudotetrahedral P3FeII-X complexes supported by tris(phosphine)borate ([PhBP3FeR]-) and phosphiniminato X-type ligands (-N=PR'3) that in combination tune the spin-crossover behavior of the system. Low-coordinate transition metal complexes such as these that undergo reversible spin-crossover remain rare, and the spin equilibria of these systems have been studied in detail by a suite of spectroscopic techniques.
\r\n", "date": "2016", "date_type": "degree", "id_number": "CaltechTHESIS:02242016-013157998", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:02242016-013157998", "related_url": { "items": [ { "description": "Article adapted for Chapter 2", "type": "doi", "url": "http://dx.doi.org/10.1021/ja4114962" }, { "description": "Article adapted for Chapter 3", "type": "doi", "url": "http://dx.doi.org/10.1021/jacs.5b04738" }, { "description": "Article adapted for Chapter 5", "type": "doi", "url": "http://dx.doi.org/10.1002/anie.201301202" }, { "description": "Article adapted for Chapter 5", "type": "doi", "url": "http://dx.doi.org/10.1126/science.1226458" } ] }, "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "suggestions": "Restricted to Caltech community only until 1 January 2017. Released 13 February 2017.", "deposited_by": "Sidney Creutz", "deposited_on": "2016-03-01 22:58:17", "doi": "10.7907/Z92V2D1M ", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "jpeters@caltech.edu", "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "mo@caltech.edu", "id": "Okumura-M", "name": { "family": "Okumura", "given": "Mitchio" }, "role": "chair" }, { "email": "gcfu@caltech.edu", "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "role": "member" }, { "email": "agapie@caltech.edu", "id": "Agapie-T", "name": { "family": "Agapie", "given": "Theodor" }, "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_defense_date": "2016-02-08", "gradofc_approval_date": "2016-02-29", "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": "2016", "author_list": "Creutz, Sidney E.", "advisor_list": "Peters, Jonas C.", "comittee_list": "Okumura, Mitchio; Fu, Gregory C.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/9299", "eprint_id": 9299, "rev_number": 34, "documents": [ { "id": "/id/document/62236", "doc_id": 62236, "rev_number": 4, "files": [ { "id": "/id/file/174406", "fileid": 174406, "datasetid": "document", "objectid": 62236, "filename": "Rittle_Thesis_edited.pdf", "mime_type": "application/pdf", "hash": "032ee1201fde9190fb83c6daf79c1a96", "hash_type": "MD5", "filesize": 11451089, "mtime": "2015-12-02 23:53:19", "url": "/9299/9/Rittle_Thesis_edited.pdf" } ], "eprint_id": 9299, "pos": 9, "placement": 9, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", 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complexes", "abstract": "The activation of Fe-coordinated N2 via the formal addition of hydrogen atom equivalents is explored in this thesis. These reactions may occur in nitrogenase enzymes during the biological conversion of N2 to NH3. To understand these reactions, the N2 reactivity of a series of molecular Fe(N2) platforms is investigated. A trigonal pyramidal, carbon-ligated FeI complex was prepared that displays a similar geometry to that of the resting state 'belt' Fe atoms of nitrogenase. Upon reduction, this species was shown to coordinate N2, concomitant with significant weakening of the C-Fe interaction. This hemilability of the axial ligand may play a critical role in mediating the interconversion of Fe(NxHy) species during N2 conversion to NH3. In fact, a trigonal pyramidal borane-ligated Fe complex was shown to catalyze this transformation, generating up to 8.49 equivalents of NH3. To shed light on the mechanistic details of this reaction, protonation of a borane-ligated Fe(N2) complex was investigated and found to give rise to a mixture of species that contains an iron hydrazido(2-) [Fe(NNH2)] complex. The identification of this species is suggestive of an early N-N bond cleavage event en route to NH3 production, but the highly-reactive nature of this complex frustrated direct attempts to probe this possibility. A structurally-analogous silyl-ligated Fe(N2) complex was found to react productively with hydrogen atom equivalents, giving rise to an isolable Fe(NNH2) species. Spectroscopic and crystallographic studies benefited from the enhanced stability of this complex relative to the borane analogue. One-electron reduction of this species initiates a spontaneous disproportionation reaction with an iron hydrazine [Fe(NH2NH2)] complex as the predominant reaction product. This transformation provides support for an Fe-mediated N2 activation mechanism that proceeds via a late N-N bond cleavage. In hopes of gaining more fundamental insight into these reactions, a series of Fe(CN) complexes were prepared and reacted with hydrogen-atom equivalents. Significant quantities of CH4 and NH3 are generated in these reactions as a result of complete C-N bond activation. A series of Fe(CNHx) were found to be exceptionally stable and may be intermediates in these reactions. The stability of these compounds permitted collection of thermodynamic parameters pertinent to the unique N-H bonds. This data is comparatively discussed with the theoretically-predicted data of the N2-derived Fe(NNHx) species. Exceptionally-weak N-H bond enthalpies are found for many of these compounds, and sheds light on their short-lived nature and tendency to evolve H2. As a whole, these works both establish and provide a means to understand Fe-mediated N2 activation via the addition of hydrogen atom equivalents.", "date": "2016", "date_type": "degree", "id_number": "CaltechTHESIS:12012015-124453213", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:12012015-124453213", "related_url": { "items": [ { "description": "Article adapted for ch. 2", "type": "doi", "url": "http://dx.doi.org/10.1038/nature12435" }, { "description": "Article adapted for ch. 2", "type": "doi", "url": "http://dx.doi.org/10.1021/jacs.5b03432" }, { "description": "Article adapted for ch. 3", "type": "doi", "url": "http://dx.doi.org/10.1073/pnas.1310153110 " }, { "description": "Article adapted for ch. 6", "type": "doi", "url": "http://dx.doi.org/10.1021/ja507217v" } ] }, "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "suggestions": "Restricted to Caltech community only until 1 January 2017. Released 1/12/2017.", "deposited_by": "Jonathan Rittle", "deposited_on": "2015-12-04 23:19:48", "doi": "10.7907/Z9QJ7F7D", "alt_title": { "items": [ "Proton-Coupled Reduction of N2 Facilitated by Molecular Fe Complexes" ] }, "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "jpeters@caltech.edu", "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "chair" }, { "email": "agapie@caltech.edu", "id": "Agapie-T", "name": { "family": "Agapie", "given": "Theodor" }, "role": "member" }, { "email": "dcrees@caltech.edu", "id": "Rees-D-C", "name": { "family": "Rees", "given": "Douglas C." }, "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_defense_date": "2015-11-09", "gradofc_approval_date": "2015-12-04", "thesis_awards": "The Herbert Newby Mccoy Award, 2016", "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": "2016", "author_list": "Rittle, Jonathan Daniel", "advisor_list": "Peters, Jonas C.", "comittee_list": "Gray, Harry B.; Agapie, Theodor; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/8746", "eprint_id": 8746, "rev_number": 101, "documents": [ { "id": "/id/document/53734", "doc_id": 53734, "rev_number": 6, "files": [ { "id": "/id/file/154823", "fileid": 154823, "datasetid": "document", "objectid": 53734, "filename": "Fong_Henry_2015_thesis.pdf", "mime_type": "application/pdf", "hash": "c8fc2c615e1ae858b25af624bd0d8ec6", "hash_type": "MD5", "filesize": 5078837, "mtime": "2014-12-17 03:24:37", "url": "/8746/13/Fong_Henry_2015_thesis.pdf" } ], "eprint_id": 8746, "pos": 13, "placement": 13, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", 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"0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/53734" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/53734" }, { "type": "http://eprints.org/relation/issmallThumbnailVersionOf", "uri": "/id/document/53734" } ] } }, { "id": "/id/document/129468", "doc_id": 129468, "rev_number": 1, "files": [ { "id": "/id/file/374904", "fileid": 374904, "datasetid": "document", "objectid": 129468, "filename": "indexcodes.txt", "mime_type": "text/plain", "hash": "8b67670eb2adfdf43e65452c22ccba2a", "hash_type": "MD5", "filesize": 32486, "mtime": "2021-06-24 03:50:11", "url": "/8746/18/indexcodes.txt" } ], "eprint_id": 8746, "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/53734" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/53734" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/53734" } ] } } ], "eprint_status": "archive", "userid": 10452, "dir": "disk0/00/00/87/46", "datestamp": "2014-12-19 19:20:24", "lastmod": "2023-11-08 18:46:52", "status_changed": "2014-12-19 19:20:24", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "fonghenry@gmail.com", "id": "Fong-Henry", "name": { "family": "Fong", "given": "Henry" }, "show_email": "NO" } ] }, "title": "Metallaboratrane Facilitated E\u2012H Bond Activation and Hydrogenation Catalysis", "ispublished": "unpub", "full_text_status": "public", "keywords": "Metallaboratrane; hydrogenation catalysis; inorganic chemistry; carbon dioxide", "abstract": "The E\u2012H bond activation chemistry of tris-phosophino-iron and -cobalt metallaboratranes is discussed. The ferraboratrane complex (TPB)Fe(N2) heterolytically activates H\u2012H and the C\u2012H bonds of formaldehyde and arylacetylenes across an Fe\u2012B bond. In particular, H\u2012H bond cleavage at (TPB)Fe(N2) is reversible and affords the iron-hydride-borohydride complex (TPB)(\u03bc\u2012H)Fe(L)(H) (L = H2, N2). (TPB)(\u03bc\u2012H)Fe(L)(H) and (TPB)Fe(N2) are competent olefin and arylacetylene hydrogenation catalysts. Stoichiometric studies indicate that the B\u2012H unit is capable of acting as a hydride shuttle in the hydrogenation of olefin and arylacetylene substrates. The heterolytic cleavage of H2 by the (TPB)Fe system is distinct from the previously reported (TPB)Co(H2) complex, where H2 coordinates as a non-classical H2 adduct based on X-ray, spectroscopic, and reactivity data. The non-classical H2 ligand in (TPB)Co(H2) is confirmed in this work by single crystal neutron diffraction, which unequivocally shows an intact H\u2012H bond of 0.83 \u00c5 in the solid state. The neutron structure also shows that the H2 ligand is localized at two orientations on cobalt trans to the boron. This localization in the solid state contrasts with the results from ENDOR spectroscopy that show that the H2 ligand freely rotates about the Co\u2012H2 axis in frozen solution. Finally, the (TPB)Fe system, as well as related tris-phosphino-iron complexes that contain a different apical ligand unit (Si, PhB, C, and N) in place of the boron in (TPB)Fe, were studied for CO2 hydrogenation chemistry. The (TPB)Fe system is not catalytically competent, while the silicon, borate, carbon variants, (SiPR3)Fe, (PhBPiPr3)Fe, and (CPiPr3)Fe, respectively, are catalysts for the hydrogenation of CO2 to formate and methylformate. The hydricity of the CO2 reactive species in the silatrane system (SiPiPr3)Fe(N2)(H) has been experimentally estimated. ", "date": "2015", "date_type": "degree", "id_number": "CaltechTHESIS:12152014-181907516", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:12152014-181907516", "related_url": { "items": [ { "description": "Article adapted for ch. 2", "type": "doi", "url": "http://dx.doi.org/10.1021/om400281v" }, { "description": "Article adapted for ch. 3", "type": "doi", "url": "http://dx.doi.org/10.1021/ja508117h" }, { "description": "Article adapted for ch. 4", "type": "doi", "url": "http://dx.doi.org/10.1021/ic502508p" } ] }, "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "local_group": { "items": [ "JCAP" ] }, "suggestions": "Restricted to Caltech community only until 1 December 2015. Released Dec. 14, 2015.", "deposited_by": "Henry Fong", "deposited_on": "2014-12-19 19:20:24", "doi": "10.7907/Z9TX3C9P", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "jpeters@caltech.edu", "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "agapie@caltech.edu", "id": "Agapie-T", "name": { "family": "Agapie", "given": "Theodor" }, "role": "chair" }, { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "member" }, { "email": "reisman@caltech.edu", "id": "Reisman-S-E", "name": { "family": "Reisman", "given": "Sarah 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_defense_date": "2014-12-05", "gradofc_approval_date": "2014-12-17", "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": "2015", "author_list": "Fong, Henry", "advisor_list": "Peters, Jonas C.", "comittee_list": "Agapie, Theodor; Gray, Harry B.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/7959", "eprint_id": 7959, "rev_number": 35, "documents": [ { "id": "/id/document/43398", "doc_id": 43398, "rev_number": 4, "files": [ { "id": "/id/file/129291", "fileid": 129291, "datasetid": "document", "objectid": 43398, "filename": "Anderson_John_Thesis2014.pdf", "mime_type": "application/pdf", "hash": "39e81a6f076fb526c427af6c30d73d1c", "hash_type": "MD5", "filesize": 6614671, "mtime": "2013-10-08 16:40:44", "url": "/7959/1/Anderson_John_Thesis2014.pdf" } ], "eprint_id": 7959, "pos": 1, "placement": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", 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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/43398" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/43398" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/43398" } ] } } ], "eprint_status": "archive", "userid": 10046, "dir": "disk0/00/00/79/59", "datestamp": "2015-01-07 19:53:10", "lastmod": "2023-11-08 00:44:05", "status_changed": "2015-01-07 19:53:10", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "jsa312@gmail.com", "id": "Anderson-John-Stuart", "name": { "family": "Anderson", "given": "John Stuart" }, "show_email": "YES" } ] }, "title": "Catalytic Conversion of Nitrogen to Ammonia by an Iron Model Complex", "ispublished": "unpub", "full_text_status": "public", "keywords": "Iron, Nitrogen Fixation, Nitrogenase", "abstract": "Threefold symmetric Fe phosphine complexes have been used to model the structural and functional aspects of biological N2 fixation by nitrogenases. Low-valent bridging Fe-S-Fe complexes in the formal oxidation states Fe(II)Fe(II), Fe(II)/Fe(I), and Fe(I)/Fe(I) have been synthesized which display rich spectroscopic and magnetic behavior. A series of cationic tris-phosphine borane (TPB) ligated Fe complexes have been synthesized and been shown to bind a variety of nitrogenous ligands including N2H4, NH3, and NH2
Treatment of an anionic FeN2 complex with excess acid also results in the formation of some NH3, suggesting the possibility of a catalytic cycle for the conversion of N2 to NH3 mediated by Fe. Indeed, use of excess acid and reductant results in the formation of seven equivalents of NH3 per Fe center, demonstrating Fe mediated catalytic N2 fixation with acids and protons for the first time. Numerous control experiments indicate that this catalysis is likely being mediated by a molecular species.
\r\n\r\nA number of other phosphine ligated Fe complexes have also been tested for catalysis and suggest that a hemi-labile Fe-B interaction may be critical for catalysis. Additionally, various conditions for the catalysis have been investigated. These studies further support the assignment of a molecular species and delineate some of the conditions required for catalysis.
\r\n\r\nFinally, combined spectroscopic studies have been performed on a putative intermediate for catalysis. These studies converge on an assignment of this new species as a hydrazido(2-) complex. Such species have been known on group 6 metals for some time, but this represents the first characterization of this ligand on Fe. Further spectroscopic studies suggest that this species is present in catalytic mixtures, which suggests that the first steps of a distal mechanism for N2 fixation are feasible in this system.
", "date": "2014", "date_type": "degree", "id_number": "CaltechTHESIS:09182013-164526961", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:09182013-164526961", "related_url": { "items": [ { "description": "Article adapted for ch. 3", "type": "doi", "url": "http://dx.doi.org/10.1021/ja307714m" }, { "description": "Article adapted for ch. 4", "type": "doi", "url": "http://dx.doi.org/10.1038/nature12435" } ] }, "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "GM070757" }, { "agency": "Gordon and Betty Moore Foundation" }, { "agency": "NSF Graduate Research Fellowship" } ] }, "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "deposited_by": "John Anderson", "deposited_on": "2015-01-07 19:53:10", "doi": "10.7907/NS23-B474", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "jonas.peters@gmail.com", "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "chair" }, { "email": "agapie@caltech.edu", "id": "Agapie-T", "name": { "family": "Agapie", "given": "Theodor" }, "role": "member" }, { "email": "stoltz@caltech.edu", "id": "Stoltz-B-M", "name": { "family": "Stoltz", "given": "Brian M." }, "role": "member" }, { "email": "jonas.peters@gmail.com", "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "2013-09-03", "gradofc_approval_date": "2013-11-20", "thesis_awards": "The Herbert Newby McCoy Award, 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": "Anderson, John Stuart", "advisor_list": "Peters, Jonas C.", "comittee_list": "Bercaw, John E.; Agapie, Theodor; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/7777", "eprint_id": 7777, "rev_number": 44, "documents": [ { "id": "/id/document/39451", "doc_id": 39451, "rev_number": 2, "files": [ { "id": "/id/file/121282", "fileid": 121282, "datasetid": "document", "objectid": 39451, "filename": "lightbox.jpg", "mime_type": "image/png", "hash": "33be122d5025d464fe08888c0cd89e19", "hash_type": "MD5", "filesize": 17755, "mtime": "2013-05-31 18:26:11", "url": "/7777/7/lightbox.jpg" } ], "eprint_id": 7777, "pos": 7, "placement": 7, "mime_type": "image/png", "format": "other", "format_desc": "Thumbnails conversion from application/pdf to thumbnail_lightbox", "language": "en", 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"media_sample_stop": "0", "content": "release" }, { "id": "/id/document/128293", "doc_id": 128293, "rev_number": 1, "files": [ { "id": "/id/file/373729", "fileid": 373729, "datasetid": "document", "objectid": 128293, "filename": "indexcodes.txt", "mime_type": "text/plain", "hash": "fbf099575b32583a8d44b0505f3fee91", "hash_type": "MD5", "filesize": 39323, "mtime": "2021-06-24 02:45:15", "url": "/7777/22/indexcodes.txt" } ], "eprint_id": 7777, "pos": 22, "placement": 22, "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/39458" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/39458" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/39458" } ] } } ], "eprint_status": "archive", "userid": 9904, "dir": "disk0/00/00/77/77", "datestamp": "2014-12-01 18:57:19", "lastmod": "2023-11-08 00:44:05", "status_changed": "2014-12-01 18:57:19", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "daniel.l.m.suess@gmail.com", "id": "Suess-Daniel-Leif-Migdow", "name": { "family": "Suess", "given": "Daniel Leif Migdow" }, "show_email": "YES" } ] }, "title": "Reactions of Small Molecules Facilitated by Metal-Acceptor Interactions", "ispublished": "unpub", "full_text_status": "public", "keywords": "Inorganic chemistry", "abstract": "The role of metal-acceptor interactions arising from M\u2013BR3 and M\u2013PR3 bonding is discussed with respect to reactions between first-row transition metals and N2, H2, and CO. Thermally robust, S = 1/2 (TPB)Co(H2) and (TPB)Co(N2) complexes (TPB = tris(2- (diisopropylphosphino)phenyl)borane) are described and the energetics of N2 and H2 binding are measured. The H2 and N2 ligands are bound more weakly in the (TPB)Co complexes than in related (SiP3)M(L) complexes (SiP3 = tris(2- (diisopropylphosphino)phenyl)silyl). Comparisons within and between these two ligand platforms allow for the factors that affect N2 (and H2) binding and activation to be delineated. The characterization and reactivity of (DPB)Fe complexes (DPB = bis(2- (diisopropylphosphino)phenyl)phenylborane) in the context of N2 functionalization and E\u2013H bond addition (E = H, C, N, Si) are described. This platform allows for the one-pot transformation of free N2 to an Fe hydrazido(-) complex via an Fe aminoimide intermediate. The principles learned from the N2 chemistry using (DPB)Fe are applied to CO reduction on the same system. The preparation of (DPB)Fe(CO)2 is described as well as its reductive functionalization to generate an unprecedented Fe dicarbyne. The bonding in this highly covalent complex is discussed in detail. Initial studies of the reactivity of the Fe dicarbyne reveal that a CO-derived olefin is released upon hydrogenation. Alternative approaches to uncovering unusual reactivity using metal- acceptor interactions are described in Chapters 5 and 6, including initial studies on a new \u03c0-accepting tridentate diphosphinosulfinyl ligand and strategies for designing ligands that undergo site-selective metallation to generate heterobimetallic complexes.", "date": "2013", "date_type": "degree", "id_number": "CaltechTHESIS:05302013-182601874", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:05302013-182601874", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "deposited_by": "Daniel Suess", "deposited_on": "2014-12-01 18:57:19", "doi": "10.7907/Q4B0-AG41", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "jpeters@caltech.edu", "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "chair" }, { "email": "reisman@caltech.edu", "id": "Reisman-S-E", "name": { "family": "Reisman", "given": "Sarah E." }, "role": "member" }, { "email": "agapie@caltech.edu", "id": "Agapie-T", "name": { "family": "Agapie", "given": "Theodor" }, "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_defense_date": "2013-05-17", "gradofc_approval_date": "2013-06-03", "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": "2013", "author_list": "Suess, Daniel Leif Migdow", "advisor_list": "Peters, Jonas C.", "comittee_list": "Bercaw, John E.; Reisman, Sarah E.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/6770", "eprint_id": 6770, "rev_number": 30, "documents": [ { "id": "/id/document/14079", "doc_id": 14079, "rev_number": 8, "files": [ { "id": "/id/file/90663", "fileid": 90663, "datasetid": "document", "objectid": 14079, "filename": "thesis-TAKAOKA-AYUMI.pdf", "mime_type": "application/pdf", "filesize": 6796135, "mtime": "2012-12-26 04:39:46", "url": "/6770/1/thesis-TAKAOKA-AYUMI.pdf" } ], "eprint_id": 6770, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": "thesis-TAKAOKA-AYUMI.pdf", "media_duration": "0", 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metals to stabilize complexes with unusual oxidation states and/or geometries. Initial studies with the [SiPPh3]\u2212 ligand on ruthenium established the flexibility of this ancillary ligand in stabilizing complexes with strongly trans influencing ligands in trans dispositions. A related ligand scaffold, [SiPiPr3]\u2212, was subsequently used to stabilize mononuclear complexes of Ru(I) and Os(I), the first examples to be isolated and thoroughly chracterized. EPR spectroscopy and DFT calculations supported their metalloradical character, and further studies highlighted their reactivity in both one- and two-electron redox processes. The ability of the [SiPiPr3]\u2212 scaffold to stabilize d7 metalloradicals of group 8 metals was extended to group 9 metals, and a series of d7 complexes of cobalt, rhodium, and iridium were synthesized in which their ancillary ligands, oxidation states, spin states, and geometry are conserved. Similar to the previously reported [SiPiPr3]Fe(N2) complex, the related [SiPiPr3]Ru(N2) complex was shown to exhibit N\u2212N coupling of organic azides to yield azoarenes catalytically. Detailed mechanistic studies conclusively showed that the Ru(III) imide species, whose iron analog is the key intermediate in the [SiPiPr3]Fe system, is not involved in the mechanism for the [SiPiPr3]Ru system. Instead, a mechanism in which free nitrene is released during the catalytic cyle is favored. Finally, hybrid ligands with multiple thioether donors in place of phosphine donors on the [SiPR3]\u2212 scaffold were synthesized to stabilize a number of dinitrogen complex of iron. These complexes featured rare examples of S\u2212Fe\u2212N2 linkages.", "date": "2012", "date_type": "degree", "id_number": "CaltechTHESIS:01202012-105759966", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:01202012-105759966", "related_url": { "items": [ { "type": "doi", "url": "http://dx.doi.org/10.1021/om900216u" }, { "type": "doi", "url": "http://dx.doi.org/10.1002/anie.201001199" }, { "type": "doi", "url": "http://dx.doi.org/10.1021/ic202079r" }, { "type": "doi", "url": "http://dx.doi.org/10.1021/ja2020907" } ] }, "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "deposited_by": "Ayumi Takaoka", "deposited_on": "2012-01-26 23:39:44", "doi": "10.7907/ZN62-KX32", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "jpeters@caltech.edu", "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "agapie@caltech.edu", "id": "Agapie-T", "name": { "family": "Agapie", "given": "Theodor" }, "role": "chair" }, { "email": "mo@its.caltech.edu", "id": "Okumura-M", "name": { "family": "Okumura", "given": "Mitchio" }, "role": "member" }, { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "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_defense_date": "2012-01-17", "gradofc_approval_date": "2012-01-26", "thesis_awards": "The Herbert Newby McCoy Award, 2012", "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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22, "format": "image/png", "language": "en", "security": "internal", "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/45481" }, { "type": "http://eprints.org/relation/ispreviewThumbnailVersionOf", "uri": "/id/document/45481" }, { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/45481" } ] } }, { "id": "/id/document/126415", "doc_id": 126415, "rev_number": 1, "files": [ { "id": "/id/file/371849", "fileid": 371849, "datasetid": "document", "objectid": 126415, "filename": "indexcodes.txt", "mime_type": "text/plain", "hash": "de2b6e005f33cbe021e3b27c4559aa43", "hash_type": "MD5", "filesize": 43844, "mtime": "2021-06-24 00:51:14", "url": "/6231/23/indexcodes.txt" } ], "eprint_id": 6231, "pos": 23, "placement": 23, "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/45480" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/45480" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/45480" } ] } } ], "eprint_status": "archive", "userid": 4266, "dir": "disk0/00/00/62/31", "datestamp": "2014-03-18 20:51:09", "lastmod": "2023-11-08 00:44:05", "status_changed": "2014-03-18 20:51:09", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "caroline.saouma@utah.edu", "id": "Saouma-Caroline-Thalia-Abdunnur", "name": { "family": "Saouma", "given": "Caroline Thalia Abdunnur" }, "show_email": "NO" } ] }, "title": "Iron Mediated Reduction Schemes for Dinitrogen and Carbon Dioxide", "ispublished": "unpub", "full_text_status": "public", "keywords": "small molecule activation; iron; nitrogen fixation; carbon dioxide reduction", "abstract": "Several mono- and diiron species that coordinate NxHy ligands have been prepared and studied, to serve as structural, spectroscopic, and/or reactivity mimics to intermediates to an alternating reduction scheme for N\u2082 (i.e., Mn-N\u2261N \u2192 Mn-HN=NH \u2192 Mn-H\u2082N-NH\u2082 \u2192 Mn + 2 NH\u2083). The reaction between [PhBPR\u2083]FeMe ([PhBPR\u2083] = (PhB(CH\u2082PR\u2082)\u2083-; R = Ph, CH\u2082Cy) and hydrazine affords {[PhBPR\u2083]Fe}\u2082(\u03bc-\u03b7\u00b9: \u03b7\u00b9-N\u2082H\u2084)(\u03bc\u00b2- \u03b7\u00b2:N\u2082H\u2082). In one instance (R = Ph), the stepwise oxidation of coordinated hydrazine to diazene, and diazene to dinitrogen is achieved, giving {[PhBPPh\u2083]Fe}\u2082(\u03bc-\u03b7\u00b9:\u03b7\u00b9-N\u2082H\u2082)(\u03bc-\u03b7 2: \u03b7 2-N2H2) and {[PhBPPh\u2083]Fe}\u2082(\u03bc-NH)\u2082, respectively.
\r\n\t\r\nAs an extension to this work, a family of complexes which feature the same auxiliary ligands (i.e., [PhBPCH2Cy\u2083]Fe(OAc)), that are all iron(II), and that only differ in the oxidation state of the nitrogenous ligand has also been prepared: {[PhBPCH2Cy\u2083]Fe(OAc)}\u2082(\u03bc-N\u2082), {[PhBPCH2Cy\u2083]Fe(OAc)}\u2082(\u03bc-N\u2082H\u2082), {[PhBPCH2Cy\u2083]Fe(OAc)}\u2082(\u03bc-N\u2082H\u2084), and {[PhBPCH2Cy\u2083]Fe(OAc)(NH\u2083).
\r\n\t\r\nTo determine whether similar species could be isolated at a single iron site, the coordination chemistry of the more crowded \u201c[PhBPmter3]Fe\u201d fragment was investigated and compared to that of the \u201c[PhBPPh3]Fe\u201d scaffold. Treatment of [PhBPmter3]FeMe with hydrazine generates the unusual 5-coordinate hydrazido complex, [PhBPmter3]Fe(\u03bc2-N2H3), which features an Fe=N \u03c0 bond. Both 5- and 6-coordinate iron complexes that coordinate hydrazine were also synthesized, and the oxidation of these hydrazine and hydrazido(-) species was explored. In most instances, oxidation results in disproportionation of the N2Hy ligand, and [PhBPR3]Fe(NH3)(OAc) (R = Ph, mter) is isolated.
\r\n\t\r\nA 5-coordinate diiron diazene redox pair of complexes, {[PhBPPh3]Fe(CO)}2(\u03bc-\u03b71:\u03b71-N2H2)0/- was also prepared and studied. The electronic structure of the Fe-NH-NH-Fe core in these complexes is unusual in that it features a highly activated diazene ligand, which is unprecedented for mid-to-late transition metals. Combined structural, spectroscopic, and computation studies indicate that there is much \u03c0-covalency within the Fe-NH-NH-Fe core, which has a similar electronic structure as butadiene.
\r\n\t\r\nWith regards to CO2 reduction, the ability of iron(I) to mediate the one- and two- electron reductions of CO2 was explored. The reaction between [PhBPCH2Cy3]Fe(PCy)3 and CO2 is solvent dependent, with oxalate formation to generate {[PhBPCH2Cy3]Fe}2(\u03bc-\u03b72:\u03b72-oxalato) being favored in THF, and decarbonylation to give {[PhBPCH2Cy3]Fe}2(\u03bc-O)(\u03bc-CO) occurring exclusively in MeCy. Studies aimed at understanding this unusual solvent-induced selectivity are presented.
\r\n", "date": "2011", "date_type": "degree", "id_number": "CaltechTHESIS:01242011-170306838", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:01242011-170306838", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "deposited_by": "Caroline Saouma", "deposited_on": "2014-03-18 20:51:09", "doi": "10.7907/46C3-BY97", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "jpeters@caltech.edu", "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "jkbarton@caltech.edu", "id": "Barton-J-K", "name": { "family": "Barton", "given": "Jacqueline K." }, "role": "chair" }, { "email": "mo@its.caltech.edu", "id": "Okumura-M", "name": { "family": "Okumura", "given": "Mitchio" }, "role": "member" }, { "email": "dcrees@caltech.edu", "id": "Rees-D-C", "name": { "family": "Rees", "given": "Douglas C." }, "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_defense_date": "2011-01-05", "gradofc_approval_date": "2011-05-31", "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": "Saouma, Caroline Thalia Abdunnur", "advisor_list": "Peters, Jonas C.", "comittee_list": "Barton, Jacqueline K.; Okumura, Mitchio; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/5592", "eprint_id": 5592, "rev_number": 28, "documents": [ { "id": "/id/document/9537", "doc_id": 9537, "rev_number": 4, "files": [ { "id": "/id/file/60293", "fileid": 60293, "datasetid": "document", "objectid": 9537, "filename": "thesis_revised_combined.pdf", "mime_type": "application/pdf", "filesize": 27989647, "mtime": "2012-12-26 03:22:31", "url": "/5592/1/thesis_revised_combined.pdf" } ], "eprint_id": 5592, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": "thesis_revised_combined.pdf", "media_duration": 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"http://eprints.org/relation/isVersionOf", "uri": "/id/document/9537" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/9537" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/9537" } ] } } ], "eprint_status": "archive", "userid": 1141, "dir": "disk0/00/00/55/92", "datestamp": "2010-03-19 17:01:13", "lastmod": "2023-11-08 00:44:05", "status_changed": "2010-03-19 17:01:13", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "nealm@caltech.edu", "id": "Mankad-Neal-P", "name": { "family": "Mankad", "given": "Neal P." }, "show_email": "YES" } ] }, "title": "Copper and Iron Complexes with Unusual Coordination Geometries Enforced by Phosphine Chelates", "ispublished": "unpub", "full_text_status": "public", "keywords": "Copper, Iron, Phosphine, Diazoalkane, Carbene, Redox, Non-innocent, Radical, Ligand, Dinitrogen fixation, Organoazide, Nitrene, Imido", "abstract": "Chelating phosphine ligands were used to enforce targeted coordination geometries onto complexes of iron and copper, thereby imparting molecular properties distinct relative to species studied previously in other geometries. The bulky bis(phosphino)borate ligand [Ph\u2082B(CH\u2082PtBu\u2082)\u2082]\u207b was used to provide trigonal planar complexes of Cu. This structural motif provided a rare opportunity for a single framework to stabilize Cu complexes in three discrete oxidation levels and allowed for the study of unique ligands including diazoalkanes, a diphenylcarbene, diarylamides, and a diarylaminyl radical. In the latter case, physical measurements (multiedge XAS and multifrequency EPR spectroscopy) and theoretical methods (DFT) were used to quantitate the delocalization of spin density between the Cu center and the NAr\u2082 unit, providing a comprehensive electronic structure picture for L\u2082CuER\u2082 (E = C or N) complexes in this system. In separate studies, trigonal bipyramidal Fe complexes were generated using the bulky, anionic tris(phosphino)silyl ligands [(2-R\u2082PC\u2086H\u2084)\u2083Si]\u207b (R = Ph or iPr). Low-valent Fe species in this system were found to activate dinitrogen, providing labile N\u2082 ligands trans to the silyl donor, including the first instance of a terminally bound N\u2082 ligated to a paramagnetic Fe center. Subsequent reactions involving these FeI-N\u2082 species and organoazides provided entry to unusual catalytic N-N coupling reactions. These reactions were found to involve reactive FeNAr intermediates, destabilized by virtue of the trigonal bipyramidal coordination geometry, which subsequently coupled bimolecularly in the N-N bond-forming step. The effects of perturbing previously studied C\u2083-symmetric pseudotetrahedral iron complexes to their trigonal bipyramidal analogues proved key to uncovering the chemistry of interest.", "date": "2010", "date_type": "degree", "id_number": "CaltechTHESIS:03112010-172248190", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:03112010-172248190", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Gayle Hammer", "deposited_by": "Neal Mankad", "deposited_on": "2010-03-19 17:01:13", "doi": "10.7907/6F4J-WE60", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "jpeters@caltech.edu", "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "chair" }, { "email": "rhg@caltech.edu", "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "role": "member" }, { "email": "reisman@caltech.edu", "id": "Reisman-S-E", "name": { "family": "Reisman", "given": "Sarah 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_defense_date": "2009-12-04", "gradofc_approval_date": "2010-03-16", "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": "Mankad, Neal P.", "advisor_list": "Peters, Jonas C.", "comittee_list": "Bercaw, John E.; Grubbs, Robert H.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/1655", "eprint_id": 1655, "rev_number": 15, "documents": [ { "id": "/id/document/2596", "doc_id": 2596, "rev_number": 3, "files": [ { "id": "/id/file/15997", "fileid": 15997, "datasetid": "document", "objectid": 2596, "filename": "MTW-Thesis.pdf", "mime_type": "application/pdf", "filesize": 10507124, "mtime": "2012-12-26 02:40:15", "url": "/1655/1/MTW-Thesis.pdf" } ], "eprint_id": 1655, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "format_desc": "MTW-Thesis.pdf", "language": "en", "security": "public", "license": "other", "main": "MTW-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/19335" }, { "type": "http://eprints.org/relation/haspreviewThumbnailVersion", "uri": "/id/document/19335" }, { "type": "http://eprints.org/relation/hasVersion", "uri": "/id/document/19335" } ] } }, { "id": "/id/document/13938", "doc_id": 13938, "rev_number": 3, "files": [ { "id": "/id/file/201582", "fileid": 201582, "datasetid": "document", "objectid": 13938, "filename": "Whited_Matthew_Thomas_2009.PDF", "mime_type": "application/pdf", "filesize": 43088, "mtime": "2016-08-22 21:15:01", "url": "/1655/2/Whited_Matthew_Thomas_2009.PDF" } ], "eprint_id": 1655, "pos": 2, "format": "application/pdf", "language": "en", "security": "internal", "license": "other", "main": "Whited_Matthew_Thomas_2009.PDF", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "approvalform" }, { "id": "/id/document/19335", "doc_id": 19335, "rev_number": 2, "files": [ { "id": "/id/file/15995", "fileid": 15995, "datasetid": "document", "objectid": 19335, "filename": "preview.png", "mime_type": "image/png", "hash": "56c44aa7cdf71be530b1b4daa4b29958", "hash_type": "MD5", "filesize": 13523, "mtime": "2012-12-26 02:40:15", "url": "/1655/3/preview.png" } ], "eprint_id": 1655, "pos": 3, "placement": 3, "mime_type": "image/png", "format": "image/png", "language": "en", "security": "validuser", "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/2596" }, { "type": "http://eprints.org/relation/ispreviewThumbnailVersionOf", "uri": "/id/document/2596" }, { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/2596" } ] } }, { "id": "/id/document/121007", "doc_id": 121007, "rev_number": 1, "files": [ { "id": "/id/file/366396", "fileid": 366396, "datasetid": "document", "objectid": 121007, "filename": "indexcodes.txt", "mime_type": "text/plain", "hash": "1f268bad1bd7a5dc320172a8c4d3f534", "hash_type": "MD5", "filesize": 41007, "mtime": "2021-06-23 21:13:58", "url": "/1655/4/indexcodes.txt" } ], "eprint_id": 1655, "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/2596" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/2596" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/2596" } ] } } ], "eprint_status": "archive", "userid": 2, "dir": "disk0/00/00/16/55", "datestamp": "2009-05-13", "lastmod": "2023-11-08 00:44:05", "status_changed": "2009-09-25 02:11:02", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "mwhited@carleton.edu", "id": "Whited-Matthew-Thomas", "name": { "family": "Whited", "given": "Matthew Thomas" }, "orcid": "0000-0002-1193-9078", "show_email": "NO" } ] }, "title": "Synthetic and Mechanistic Studies of Small-Molecule Activation at Low-Valent Iron, Cobalt, and Iridium Centers", "ispublished": "unpub", "full_text_status": "public", "keywords": "C-H activation; carbene; dinitrogen reduction; group transfer; nucleophilic-at-metal carbene; small-molecule activation", "abstract": "The preparation of transition-metal systems for catalytic multielectron transformations of small molecules remains a significant challenge for synthetic chemists. The realization of new transformations often depends critically on the design of frameworks capable of stabilizing unusual oxidation states and molecular geometries, providing a frontier molecular-orbital landscape that is well suited to interact with the molecules of interest. This thesis has sought to address two particularly noteworthy challenges in the field of small-molecule activation, dinitrogen reduction and C\u2013H bond functionalization, through judicious ligand choice and design.
\r\n\r\nChapters 2 and 3 describe the syntheses of new tri- and tetradentate hybrid ligands incorporating a single X-type donor (amido or silyl) and multiple phosphine donors designed to stabilize low oxidation states at iron and cobalt and support dinitrogen reduction and other multielectron redox transformations. While the amidophosphine ligands do allow access to unusual monovalent iron and cobalt complexes, the isolation of dinitrogen adducts supported by these ligands remains elusive and the weakness of the silicon\u2013nitrogen bond makes the complexes prone to decomposition. In contrast, the tris(phosphino)silyl ligands presented in Chapter 3 afford straightforward access to the first terminally bonded dinitrogen complexes of monovalent iron, and the structure of these and related complexes are described along with preliminary experiments showing that protonolysis of the iron(I)\u2013dinitrogen complexes produces hydrazine in reasonable stoichiometric yields.
\r\n\r\nChapters 4 through 7 address the functionalization of ether and amine C\u2013H bonds by a double C\u2013H activation route. Chapter 4 describes the investigation of reactivity of low-valent, pincer-supported iridium species with a variety of ethers, leading to a number of selective C\u2013H, C\u2013C, and C\u2013O bond cleavage events, affording in several cases iridium carbene complexes by double C\u2013H activation and loss of dihydrogen.
\r\n\r\nChapter 5 presents an exploration of the electronic structure of the unusual square-planar iridium(I) alkoxycarbenes and their nucleophilic activation of several heterocumulene substrates, leading to multiple-bond metathesis events promoted by metal- rather than ligand-initiated reactivity. Chapter 6 describes the discovery of new atom and group transfer reactions from diazo reagents to the alkoxycarbenes and the implementation of these reactions in an unprecedented catalytic cycle for C=E bond formation by multiple C\u2013H activations.
\r\n\r\nChapter 7 explores the related reactivity of a low-valent pincer iridium complex with methyl amines and the reactivity of the resulting iridium(III) dihydrido aminocarbenes, which is shown to diverge substantially from that observed for the iridium(I) carbene species.
\r\n", "date": "2009", "date_type": "degree", "id_number": "CaltechETD:etd-05062009-173812", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechETD:etd-05062009-173812", "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": "2009-05-13", "doi": "10.7907/4N3R-5194", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "rhg@caltech.edu", "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "role": "advisor" }, { "email": "jpeters@caltech.edu", "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "jkbarton@caltech.edu", "id": "Barton-J-K", "name": { "family": "Barton", "given": "Jacqueline K." }, "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": "agapie@caltech.edu", "id": "Agapie-T", "name": { "family": "Agapie", "given": "Theodor" }, "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": "2009-05-06", "thesis_defense_date": "2009-04-17", "thesis_approved_date": "2009-05-13", "gradofc_approval_date": "2009-05-12", "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": "Whited, Matthew Thomas", "advisor_list": "Grubbs, Robert H. and Peters, Jonas C.", "comittee_list": "Barton, Jacqueline K.; Dougherty, Dennis A.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/2364", "eprint_id": 2364, "rev_number": 11, "documents": [ { "id": "/id/document/4499", "doc_id": 4499, "rev_number": 3, "files": [ { "id": "/id/file/25912", "fileid": 25912, "datasetid": "document", "objectid": 4499, "filename": "CCL_Thesis_Corrected.pdf", "mime_type": "application/pdf", "filesize": 3466451, "mtime": "2012-12-26 02:50:38", "url": "/2364/1/CCL_Thesis_Corrected.pdf" } ], "eprint_id": 2364, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": "CCL_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/21065" }, { "type": "http://eprints.org/relation/haspreviewThumbnailVersion", "uri": "/id/document/21065" }, { "type": "http://eprints.org/relation/hasVersion", "uri": "/id/document/21065" } ] } }, { "id": "/id/document/16203", "doc_id": 16203, "rev_number": 3, "files": [ { "id": "/id/file/203252", "fileid": 203252, "datasetid": "document", "objectid": 16203, "filename": "Lu_Connie_Chih_2006.PDF", "mime_type": "application/pdf", "filesize": 41817, "mtime": "2016-08-22 21:15:56", "url": "/2364/2/Lu_Connie_Chih_2006.PDF" } ], "eprint_id": 2364, "pos": 2, "format": "application/pdf", "language": "en", "security": "internal", "license": "other", "main": "Lu_Connie_Chih_2006.PDF", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "approvalform" }, { "id": "/id/document/21065", "doc_id": 21065, "rev_number": 2, "files": [ { "id": "/id/file/25910", "fileid": 25910, "datasetid": "document", "objectid": 21065, "filename": "preview.png", "mime_type": "image/png", "hash": "f7245abc0ad68072ce4611c5722cde8d", "hash_type": "MD5", "filesize": 7983, "mtime": "2012-12-26 02:50:38", "url": "/2364/3/preview.png" } ], "eprint_id": 2364, "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/4499" }, { "type": "http://eprints.org/relation/ispreviewThumbnailVersionOf", "uri": "/id/document/4499" }, { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/4499" } ] } }, { "id": "/id/document/122760", "doc_id": 122760, "rev_number": 1, "files": [ { "id": "/id/file/368158", "fileid": 368158, "datasetid": "document", "objectid": 122760, "filename": "indexcodes.txt", "mime_type": "text/x-c", "hash": "f09bf810d8a650518d20c8588e379425", "hash_type": "MD5", "filesize": 35117, "mtime": "2021-06-23 22:06:30", "url": "/2364/4/indexcodes.txt" } ], "eprint_id": 2364, "pos": 4, "placement": 4, "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/4499" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/4499" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/4499" } ] } } ], "eprint_status": "archive", "userid": 2, "dir": "disk0/00/00/23/64", "datestamp": "2006-06-02", "lastmod": "2023-11-08 00:44:05", "status_changed": "2009-09-25 02:35:50", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "clu@umn.edu", "id": "Lu-Connie-Chih", "name": { "family": "Lu", "given": "Connie Chih" }, "orcid": "0000-0002-5162-9250", "show_email": "YES" } ] }, "title": "The Chemistry of Tris(phosphino)borate Manganese and Iron Platforms", "ispublished": "unpub", "full_text_status": "public", "keywords": "coordination chemistry; small molecule activation", "abstract": "The coordination chemistry of monovalent and divalent manganese complexes supported by the anionic tris(phosphino)borate ligand [PhBPiPr3] is presented. The halide complexes, [PhBPiPr3]MnCl and [PhBPiPr3]MnI, have been characterized by XRD, SQUID magnetometry, and EPR spectroscopy. The halide [PhBPiPr3]MnI serves as a precursor to manganese azide, alkyl, and amide species: [PhBPiPr3]Mn(N3), [PhBPiPr3]Mn(CH2Ph), [PhBPiPr3]Mn(Me), [PhBPiPr3]Mn(NH(2,6-iPr2Ph)), [PhBPiPr3]Mn(dbabh), and [PhBPiPr3]Mn(1-Ph(isoindolate)). Collectively, they represent an uncommon motif of low-coordinate polyphosphine-supported manganese species. Some of our synthetic efforts to generate [PhBPiPr3]Mn?Nx species are described, as are theoretical DFT studies that probe the electronic viability of these multiply bonded target structures.
\r\n\r\nTwo tris(phosphino)borate ligands, [PhBPter3] and [PhBPCH2Cy3] are introduced that feature terphenyl and methylcyclohexyl groups on the phosphine arms, respectively. The iron chlorides, [PhBPter3]FeCl and [PhBPCH2Cy3]FeCl, have been prepared as precursors to iron nitrides. Addition of the nitride transfer reagent Li(dbabh) to [PhBPCH2Cy3]FeCl produced the terminal nitride, [PhBPCH2Cy3]Fe(N). The 15N NMR spectrum of the labeled species, [PhBPCH2Cy3]Fe(15N), contains a peak at 929 ppm, consistent with a terminal nitride functionality. Mossbauer spectroscopy of the nitride shows a low isomer shift value of 0.34(1) mm/s and an exceptionally large quadrupole splitting of 6.01(1) mm/s.
\r\n\r\nReduction of [PhBPCH2Cy3]FeCl generates a masked iron(I) species that is highly reactive. Combustion analysis of this species is consistent with \"[PhBPCH2Cy3]Fe.\" Other physical methods including VT NMR, EPR, and IR spectroscopies suggest the presence of a paramagnetic species in equilibrium with a diamagnetic species. The paramagnetic component is postulated to be an Fe(III) hydride, wherein a ligand C-H bond has been cyclometalated at the metal center. The reactivity of \"[PhBPCH2Cy3]Fe\" is consistent with iron(I). For example, its reaction with PMe3 and 1-adamantylazide affords the phosphine adduct, [PhBPCH2Cy3]Fe(PMe3), and the iron imide, [PhBPCH2Cy3]Fe(NAd), respectively. Interestingly, \"[PhBPCH2Cy3]Fe\" undergoes redox reactions with benzene to give initially a benzene adduct, {[PhBPCH2Cy3]Fe}2(mu-eta3:eta3-C6H6), which decomposes to {[PhBPCH2Cy3]Fe}2(mu-eta5:eta5-6,6'-bicyclohexadienyl) via radical C-C bond coupling. Finally, \"[PhBPCH2Cy3]Fe\" readily reduces CO2 at rt to give as the major product {[PhBPCH2Cy3]Fe}2(mu-CO)(mu-O), wherein a C=O bond has been cleaved. The minor product has not been definitively established, but one possibility is the oxalate-bridged dimer {[PhBPCH2Cy3]Fe}2(mu-eta2:eta2-O2CCO2) that results from reductive coupling of two CO2 molecules.
\r\n", "date": "2006", "date_type": "degree", "id_number": "CaltechETD:etd-06012006-151944", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechETD:etd-06012006-151944", "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": "2006-06-02", "doi": "10.7907/0DND-1J03", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "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": "jpeters@caltech.edu", "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "role": "member" }, { "email": "wag@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": "2006-06-01", "thesis_defense_date": "2006-05-26", "thesis_approved_date": "2006-06-02", "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": "2006", "author_list": "Lu, Connie Chih", "advisor_list": "Peters, Jonas C.", "comittee_list": "Bercaw, John E.; Stoltz, Brian M.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/1836", "eprint_id": 1836, "rev_number": 10, "documents": [ { "id": "/id/document/3047", "doc_id": 3047, "rev_number": 3, "files": [ { "id": "/id/file/18376", "fileid": 18376, "datasetid": "document", "objectid": 3047, "filename": "Thesis.pdf", "mime_type": "application/pdf", "filesize": 2008856, "mtime": "2012-12-26 02:42:48", "url": "/1836/1/Thesis.pdf" } ], "eprint_id": 1836, "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", "media_sample_stop": "0", "content": "final", "relation": { "items": [ { "type": "http://eprints.org/relation/hasVolatileVersion", "uri": "/id/document/19752" }, { "type": "http://eprints.org/relation/haspreviewThumbnailVersion", "uri": "/id/document/19752" }, { "type": "http://eprints.org/relation/hasVersion", "uri": "/id/document/19752" } ] } }, { "id": "/id/document/19752", "doc_id": 19752, "rev_number": 2, "files": [ { "id": "/id/file/18374", "fileid": 18374, "datasetid": "document", "objectid": 19752, "filename": "preview.png", "mime_type": "image/png", "hash": "cc64501cd06cd00e0d05533f706eb02c", "hash_type": "MD5", "filesize": 8426, "mtime": "2012-12-26 02:42:48", "url": "/1836/2/preview.png" } ], "eprint_id": 1836, "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/3047" }, { "type": "http://eprints.org/relation/ispreviewThumbnailVersionOf", "uri": "/id/document/3047" }, { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/3047" } ] } }, { "id": "/id/document/121352", "doc_id": 121352, "rev_number": 1, "files": [ { "id": "/id/file/366744", "fileid": 366744, "datasetid": "document", "objectid": 121352, "filename": "indexcodes.txt", "mime_type": "text/plain", "hash": "47533ac50ebf528f368f942150ddeb0d", "hash_type": "MD5", "filesize": 35330, "mtime": "2021-06-23 21:24:24", "url": "/1836/3/indexcodes.txt" } ], "eprint_id": 1836, "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/3047" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/3047" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/3047" } ] } } ], "eprint_status": "archive", "userid": 2, "dir": "disk0/00/00/18/36", "datestamp": "2006-05-17", "lastmod": "2023-11-08 00:44:05", "status_changed": "2009-09-25 02:16:53", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "thomas.3877@osu.edu", "id": "Thomas-Christine-Marie", "name": { "family": "Thomas", "given": "Christine Marie" }, "orcid": "0000-0001-5009-0479", "show_email": "YES" } ] }, "title": "Novel Reactivity at Iron Centers Supported by Poly(phosphino)borate Ligands", "ispublished": "unpub", "full_text_status": "public", "keywords": "coordination chemistry; synthesis", "abstract": "The reactivity of the iron(II) alkyl species [PhBPiPr3]FeMe ([PhBPiPr3] = PhB(CH2PiPr2)3-) towards Si-H bonds is presented. Reaction of [PhBPiPr3]FeMe with primary aryl silanes results in the unusual \u03b73 silane adducts [PhBPiPr3]Fe(H)(\u03b73-H2SiMeR). X-ray crystallography, Mossbauer spectroscopy, and theoretical calculations confirm this structural assignment; however, solution NMR experiments suggest a degree of fluxionality in solution.
\r\n\r\nLow valent, tris(phosphino)borate iron platforms have been shown to facilitate the activation of white phosphorus, P4. The iron(I) precursors {[PhBPiPr3]Fe}2(\u03bc-N2) and [PhBPPh3]Fe(PPh3) react with P4 to quantitatively generate {[PhBPiPr3]Fe}2(\u03bc-P4) and {[PhBPPh3]Fe}2(\u03bc-P4), respectively. These unique iron(II) dimers bridged by square P42- units have been characterized structurally and spectroscopically, and their reactivity has been examined. A simplified electronic structure calculation is presented to aid in discussion of bonding within these complexes.
\r\n\r\nMotivated by the versatility of the tris(phosphino)borate ligands, a new family of tripodal hybrid bis(phosphino)pyrazolylborate ligands, [PhBPtBu2(pz')]- ([PhBPtBu2(pz')]- = PhB(CH2PtBu2)2(pz')-), has been prepared and characterized. The synthesis, spectroscopy, and solid-state structures of four-coordinate, pseudo-tetrahedral iron(II) and cobalt(II) halide complexes supported by these ligands is presented. To compare the electron-releasing ability of these ligands with their [PhBPR3] analogues, the cyclic voltammetry of these complexes is introduced. Potential routes to a terminal cobalt or iron nitride complex via extrusion of N2 from coordinated azide and metathesis with the N-atom transfer reagent Li(dbabh) are investigated.
\r\n\r\nReduction of the [PhBPtBu2(pz')]MX halide complexes in the presence of excess phosphine generates low valent [PhBPtBu2(pz')]MI(PMe3) precursors. These precursors react with organic azides to generate cobalt(III) and iron(III) imides. Initial reactivity studies indicate that these imides are more moderately more reactive than the corresponding tris(phosphino)borate complexes. The electrochemistry of the [PhBPtBu2(pz')]FeIII(NR) imides features a quasi-reversible to fully reversible oxidation event, dependent on choice of pyrazolyl substituents and scan rate. This oxidation can be achieved chemically to generate the isolable cationic iron(IV) imides, [PhBPtBu2(pz')]FeIV(NR)+. The structural and spectroscopic characterization of these highly unusual complexes is discussed.
\r\n", "date": "2006", "date_type": "degree", "id_number": "CaltechETD:etd-05162006-201134", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechETD:etd-05162006-201134", "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": "2006-05-17", "doi": "10.7907/AGQC-8E07", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "stoltz@caltech.edu", "id": "Stoltz-B-M", "name": { "family": "Stoltz", "given": "Brian M." }, "role": "chair" }, { "email": "jkbarton@caltech.edu", "id": "Barton-J-K", "name": { "family": "Barton", "given": "Jacqueline K." }, "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": "2006-05-16", "thesis_defense_date": "2006-05-08", "thesis_approved_date": "2006-05-17", "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": "Thomas, Christine Marie", "advisor_list": "Peters, Jonas C.", "comittee_list": "Stoltz, Brian M.; Barton, Jacqueline K.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/3109", "eprint_id": 3109, "rev_number": 27, "documents": [ { "id": "/id/document/5539", "doc_id": 5539, "rev_number": 5, "files": [ { "id": "/id/file/32701", "fileid": 32701, "datasetid": "document", "objectid": 5539, "filename": "Lib-AppendixA.pdf", "mime_type": "application/pdf", "filesize": 402161, "mtime": "2012-12-26 02:57:06", "url": "/3109/1/Lib-AppendixA.pdf" } ], "eprint_id": 3109, "pos": 1, "placement": 3, "mime_type": "application/pdf", "format": "application/pdf", "format_desc": "AppendixA.pdf", "language": "en", "security": "public", "license": "other", "main": "Lib-AppendixA.pdf", 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"eprint_status": "archive", "userid": 2, "dir": "disk0/00/00/31/09", "datestamp": "2005-08-16", "lastmod": "2023-11-08 00:44:05", "status_changed": "2009-09-25 02:51:44", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Harkins-Seth-Beebe", "name": { "family": "Harkins", "given": "Seth Beebe" }, "show_email": "NO" } ] }, "title": "The Synthesis and Study of Redox-Rich, Amido-Bridged Cu\u2082N\u2082 Dicopper Complexes", "ispublished": "unpub", "full_text_status": "public", "keywords": "amido-ligand; coordination chemistry; copper(III); diamond core; dicopper; highly emissive; luminescence; redox active", "abstract": "A Cu2N2 diamond core structure supported by an [SNS]- ligand exhibits a fully reversible one-electron redox process between a reduced CuICuI, {(SNS)Cu}2, and a class III delocalized Cu1.5Cu1.5 state, {(SNS)Cu}2][B(C6H3(CF3)2)4] ([SNS]- bis(2-t-butylsulfanylphenyl)amide). The Cu\u00b7\u00b7\u00b7Cu distance compresses appreciably (~0.13 \u00c5) upon oxidation; a metal-metal distance of 2.4724(4) \u00c5 is observed in the mixed-valence molecule that is nearly identical to the dicopper CuA site found in cytochrome c oxidase. The rate of electron self-exchange ks) between the CuICuI and the Cu1.5Cu1.5 complexes was estimated to be \u2265 107 M-1s-1 by 1H NMR line-broadening analysis. The unusually large magnitude of ks reflects the minimal structural reorganization that accompanies CuICuI \u2194 Cu1.5Cu1.5 interchange.
\r\n\r\nA second generation of {(PNP)CuI}2 dimer supported by a [PNP]- ligand also has been investigated ([PNP]- = bis(2-(diisobutylphosphino)phenyl)amide). The highly emissive {(PNP)CuI}2 is characterized by a long-lived excited state (\u03c4 > 10 \u03bcs) with an unusually high quantum yield (\u03c6 > 0.65) at ambient temperature. Removal of an electron from the {(PNP)CuI}2 dimer yields a nearly isostructural, Cu1.5Cu1.5 complex {(PNP)Cu}2][B(C6H3(CF3)2)4]. With a highly reducing excited state reduction potential (~ -3.2 V vs. Fc+/Fc) as well as the availability of two reversible redox processes, these bimetallic copper systems may be interesting candidates for photochemically driven two-electron redox transformations.
\r\n\r\nStudies of Cu2N2 diamond core complexes supported by the [tBu2-PNP]- ligand revealed that the dicopper complex {(tBu2-PNP)Cu}2 can not only be oxidized by one electron to {(tBu2-PNP)Cu1.5}2][B(C6H3(CF3)2)4], but also by two-electrons to {(tBu2-PNP)Cu}2][SbF6]2 ([tBu2-PNP]- = bis(2-diisobutylphoshino-4-tbutylphenyl)amide). These Cu2N2 complexes show remarkably low structural reorganization for all oxidation states as evidenced by the solid-state molecular-structures. Based on these studies of [{(tBu2-PNP)Cu}2][SbF6]2, we propose a formulation of one CuI and one paramagnetic CuIII nuclei in compressed-tetrahedral environments in the Cu2N2 core. Spectroscopic, redox, and magnetic data are consistent with a highly covalent M2N2 core supported by a rigid ligand scaffold. These complexes are excellent mimics of the entatic state found in bimetallic copper proteins.
", "date": "2006", "date_type": "degree", "id_number": "CaltechETD:etd-08132005-093856", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechETD:etd-08132005-093856", "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": "2005-08-16", "doi": "10.7907/1X2Q-3P72", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "tirrell@caltech.edu", "id": "Tirrell-D-A", "name": { "family": "Tirrell", "given": "David A." }, "role": "chair" }, { "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" }, { "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": "2005-08-13", "thesis_defense_date": "2005-06-27", "thesis_approved_date": "2005-08-16", "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": "Harkins, Seth Beebe", "advisor_list": "Peters, Jonas C.", "comittee_list": "Tirrell, David A.; Gray, Harry B.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/2330", "eprint_id": 2330, "rev_number": 27, "documents": [ { "id": "/id/document/4419", "doc_id": 4419, "rev_number": 2, "files": [ { "id": "/id/file/25466", "fileid": 25466, "datasetid": "document", "objectid": 4419, "filename": "ThesisCh0.pdf", "mime_type": "application/pdf", "filesize": 306877, "mtime": "2012-12-26 02:50:10", "url": "/2330/1/ThesisCh0.pdf" } ], "eprint_id": 2330, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "format_desc": "ThesisCh0.pdf", "language": "en", "security": "public", "license": "other", "main": "ThesisCh0.pdf", "media_duration": "0", "media_aspect_ratio": "0", 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"metadata_visibility": "show", "creators": { "items": [ { "email": "stevenb@caltech.edu", "id": "Brown-Steven-Douglas", "name": { "family": "Brown", "given": "Steven Douglas" }, "show_email": "NO" } ] }, "title": "The Chemistry of Tris(phosphino)borate Supported Iron-Nitrogen Multiply-Bonded Linkages", "ispublished": "unpub", "full_text_status": "public", "keywords": "Iron; Multiple Bonds; Multiply Bonded Ligands; Nitrogen", "abstract": "The metallation of FeX2 (X = Cl, Br, I) salts with the strong-field [PhBP3] ([PhBP3] = PhB(CH2PPh2)3-) ligand is presented. The resulting four-coordinate, 14-electron species, [PhBP3]FeX, have been thoroughly characterized and feature high-spin (S = 2) electronic ground-states. X-ray diffraction analysis of [PhBP3]FeCl establishes a monomeric structure in the solid state.
\r\n\r\nThe one electron reduction of [PhBP3]FeCl in the presence of a triphenylphosphine cap affords a rare example of four-coordinate iron(I). This species, [PhBP3]Fe(PPh3), serves as a synthetic surrogate to a low-valent \"[PhBP3]Fe(I)\" subunit that is readily oxidized in the presence of organic azides. The resulting S = 1/2 iron(III) imides of general formula [PhBP3]Fe\u2261NR may be subsequently reduced by one electron to yield the anionic S = 0 derivatives. Exposure of the former to an atmosphere of CO results in cleavage of the Fe\u2261NR linkage to yield [PhBP3]Fe(CO)2 and free isocyanate (O=C=N-R). Dicarbonyl [PhBP3]Fe(CO)2 is itself an imide precursor and is gradually converted back to [PhBP3]Fe\u2261NR upon exposure to excess organic azide.
\r\n\r\nTolyl imide [PhBP3]Fe?N-p-tolyl readily reacts with H2 under mild conditions to undergo a step-wise Fe-Nx bond scission process to ultimately release free p-toluidine. Initially formed is the S = 2 iron(II) anilide, [PhBP3]Fe(N(H)-p-tolyl), which has been independently prepared and shown to release p-toluidine in the presence of H2. In benzene solvent the final iron containing product of the hydrogenation process is diamagnetic [PhBP3]Fe(?5-cyclohexadienyl), which is presumably formed from benzene insertion into a low-valent iron-hydride intermediate.
\r\n\r\nReduction of the ferromagnetically coupled dimer, {[PhBP3]Fe(N3)}2, yields the bridging nitride species, [{[PhBP3]Fe}2(\u03bc-N)][Na(THF)5]. This compound features two high-spin iron(II) metal centers that are so strongly antiferromagnetically coupled that a diamagnetic S = 0 ground-state is exclusively populated at room temperature. X-ray diffraction analysis reveals a bent Fe-N-Fe linkage that quantitatively releases ammonia in the presence of excess protons. Reactivity with CO and H2 is also presented, and for the latter, complete rupture of the Fe-N-Fe manifold is not observed as the presence of an additional metal center (when compared with the iron(III) imides) favors the formation of the diamagnetic bridging imide-hydride species, [{[PhBP3]Fe}2(\u03bc-NH)(\u03bc-H)][Na(THF)5].
", "date": "2005", "date_type": "degree", "id_number": "CaltechETD:etd-05312005-201150", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechETD:etd-05312005-201150", "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": "10.7907/46DN-YH09", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "stoltz@caltech.edu", "id": "Stoltz-B-M", "name": { "family": "Stoltz", "given": "Brian M." }, "role": "chair" }, { "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" }, { "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": "2005-05-31", "thesis_defense_date": "2005-05-24", "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": "Brown, Steven Douglas", "advisor_list": "Peters, Jonas C.", "comittee_list": "Stoltz, Brian M.; Gray, Harry B.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/5205", "eprint_id": 5205, "rev_number": 44, "documents": [ { "id": "/id/document/8265", "doc_id": 8265, "rev_number": 3, "files": [ { "id": "/id/file/51109", "fileid": 51109, "datasetid": "document", "objectid": 8265, "filename": "0.pdf", "mime_type": "application/pdf", "filesize": 158766, "mtime": "2012-12-26 03:16:05", "url": "/5205/1/0.pdf" } ], "eprint_id": 5205, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "format_desc": "0.pdf", "language": "en", "security": "public", "license": "other", "main": "0.pdf", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", 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"eprint_status": "archive", "userid": 2, "dir": "disk0/00/00/52/05", "datestamp": "2005-05-27", "lastmod": "2023-11-08 00:44:05", "status_changed": "2009-10-06 23:34:14", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "tbetley@gmail.com", "id": "Betley-Theodore-Alexander", "name": { "family": "Betley", "given": "Theodore Alexander" }, "orcid": "0000-0001-5946-9629", "show_email": "YES" } ] }, "title": "Coordination Chemistry from Trigonally Coordinated Iron Platforms: Chemistry Relevant to Dinitrogen Reduction", "ispublished": "unpub", "full_text_status": "public", "keywords": "Dinitrogen; Iron", "abstract": "The synthesis for a sterically encumbered, strong-field tris(diisopropylphosphino)borate ligand, [PhBPiPr3] ([PhBPiPr3] = [PhB(CH2PiPr2)3]-), is reported to probe aspects of its conformational and electronic characteristics within a host of complexes. To this end, the Tl(I) complex, [PhBPiPr3]Tl, was synthesized, characterized, and used to install the [PhBPiPr3] ligand onto complexes of Fe, Co, and Ru. The spectroscopic, electrochemical, magnetic, and structural features of these complexes are compared with similar examples.
\r\n\r\nTrigonally coordinated \"[PhBPiPr3]M\" platforms (M = Fe, Co) support both pi-acidic (N2) and pi-basic (NR2-) ligands at a fourth binding site. Methylation of monomeric [M0(N2)-] species successfully derivatizes the beta-N atom of the N2 ligand and affords the diazenido product [MII(N2Me)]. Addition of RN3 to MI(N2)MI results in oxidative nitrene transfer to generate [PhBPiPr3]M\u2261NR with concomitant N2 release.
\r\n\r\nA tetrahedrally coordinated L3Fe-Nx platform that accommodates both terminal nitride (L3FeIV\u2261N) and dinitrogen (L3FeI-N2-FeIL3) functionalities is described. The diamagnetic L3FeIV\u2261N species featured has been characterized in solution under ambient conditions by multinuclear NMR (1H, 31P, and 15N) and infrared spectroscopy. The terminal nitride complex oxidatively couples to generate the previously reported L3FeI-N2-FeIL3 species.
\r\n\r\nThe [PhBPiPr3] ligand can support a single iron or cobalt center in a pseudo-tetrahedral environment in which dinitrogen is bound in the fourth coordination site. Zero-valent metal-dinitrogen complexes have the general formula, [[PhBPiPr3]M(mu-N2)]2[Mg2+], while bridging structures can also be obtained as neutral [MI]\u2014N2\u2014[MI] or as anionic [(M)2(N2)]- species. The nature of the structural distortions observed in both [M(mu-N2)]2[Mg2+] and [Mn]\u2014N2\u2014[Mn] complexes are described. Magnetic characterization of the neutral and mixed-valence dimeric complexes reveal the complexes remain ferromagnetically coupled over all temperatures investigated.
\r\n\r\nThe coordination chemistry of group VIII metals featuring the bis(8-quinolinyl)amine (HBQA) ligand is presented. The electrochemical behavior of Fe, Ru, and Os complexes bearing the BQA ligand is reported and compared to related ligand platforms. Halide and phosphine ligand exchange reactions are examined from complexes of the type (BQA)MX(PR3)2 (M = Ru, Os). Carbonyl and dinitrogen complexes of Ru and Os are prepared from halide abstraction from divalent Ru and Os precursors. The spectroscopic and structural features of these complexes are compared with similar examples.
\r\n", "date": "2005", "date_type": "degree", "id_number": "CaltechETD:etd-05272005-103515", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechETD:etd-05272005-103515", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "suggestions": "betley@chemistry.harvard.edu", "deposited_by": "Imported from ETD-db", "deposited_on": "2005-05-27", "doi": "10.7907/PY23-ME66", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "jpeters@caltech.edu", "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "jkbarton@caltech.edu", "id": "Barton-J-K", "name": { "family": "Barton", "given": "Jacqueline K." }, "role": "chair" }, { "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": "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": "2005-05-27", "thesis_defense_date": "2005-04-18", "thesis_approved_date": "2005-05-27", "thesis_awards": "The Herbert Newby McCoy Award, 2005.", "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": "Betley, Theodore Alexander", "advisor_list": "Peters, Jonas C.", "comittee_list": "Barton, Jacqueline K.; Stoltz, Brian M.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/591", "eprint_id": 591, "rev_number": 55, "documents": [ { "id": "/id/document/885", "doc_id": 885, "rev_number": 10, "files": [ { "id": "/id/file/5557", "fileid": 5557, "datasetid": "document", "objectid": 885, "filename": "Chapter_1_text.pdf", "mime_type": "application/pdf", "filesize": 4497574, "mtime": "2012-12-26 02:30:49", "url": "/591/2/Chapter_1_text.pdf" } ], "eprint_id": 591, "pos": 2, "placement": 3, "mime_type": "application/pdf", "format": "application/pdf", "format_desc": "Chapter 1: Background and introduction to cobalt tris(phosphino)borate chemistry", "language": "en", "security": 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] }, "title": "Low Spin Pseudotetrahedral Cobalt Tris(phosphino)borate Complexes", "ispublished": "unpub", "full_text_status": "public", "keywords": "imide; imido; low spin; nitride; pseudotetrahedral", "abstract": "A synthetic protocol is developed for the preparation of a thallium complex featuring the tris(phosphino)borate ligand [PhBP3] ([PhBP3] = [PhB(CH2PPh2)3]-). The transmetallating reagent, [PhBP3]Tl, is characterized by single crystal X-ray diffraction and solution NMR spectroscopy, and is the first example of a stable homoleptic Tl(I)-phosphine complex.
\r\n\r\nThe synthesis and characterization of [PhBP3]Co-X (X = I, Br or Cl) is discussed. These halide complexes are structurally characterized and magnetic investigations establish that they are low spin when monomeric. The low spin iodide complex is a monomer in solution and in the solid state. The other halides exhibit a monomer/dimer equilibrium that complicates their magnetic behavior. Theoretical calculations help provide a rationale as to why these pseudotetrahedral species are low spin. A classic high spin species supported by [PhBP3] is compared to the low spin complexes.
\r\n\r\nSpin state control involving pseudotetrahedral [PhBP3]Co(II) complexes is explored. Both high and low spin, as well as spin crossover, complexes are synthesized and structurally characterized. The complexes are discussed in terms of the relationship between local geometry and spin state. Changing the axial or tripodal ligand can cause a different spin state to be favored. Since the energy difference between the states is small, ligand changes at remote positions from the metal center have a significant effect on spin crossover phenomena. Theoretical calculations help illuminate why the low spin state is preferred for many of the complexes.
\r\n\r\nThe first examples of cobalt imide complexes ([PhBP3]Co\u2261NR (R = aryl or alkyl)) are prepared and they are supported by the [PhBP3] ligand. These diamagnetic species are evaluated by NMR and single crystal X-ray diffraction. Theoretical studies suggest that they have a similar molecular orbital bonding scheme as the previously prepared group 9 imides.
\r\n\r\nA cobalt \u03bc2-bridging nitride complex (([PhBP3]Co)2(\u03bc-N)) is synthesized and structurally characterized. This mixed-valence species is evaluated by magnetometry to determine its ground state, which is low spin (S = \u00bd).
\r\n\r\nSeveral cobalt diazoalkane complexes are prepared. These diamagnetic species adopt two different bonding modes depending on the nature of the diazoalkane ligand.
", "date": "2005", "date_type": "degree", "id_number": "CaltechETD:etd-02102005-144940", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechETD:etd-02102005-144940", "related_url": { "items": [ { "description": "Article adapted for Ch. 2", "type": "doi", "url": "https://doi.org/10.1039/B104447H" }, { "description": "Article adapted for Ch. 3", "type": "doi", "url": "https://doi.org/10.1021/ja026433e" }, { "description": "Article adapted for Ch. 4", "type": "doi", "url": "https://doi.org/10.1021/ja036198f" }, { "description": "Article adapted for Ch. 5 and 7", "type": "doi", "url": "https://doi.org/10.1021/ja026852b" } ] }, "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": "2005-02-14", "doi": "10.7907/5WNW-R611", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "jpeters@caltech.edu", "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "chair" }, { "email": "dmacmill@caltech.edu", "id": "MacMillan-D-W-C", "name": { "family": "MacMillan", "given": "David W. C." }, "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": "2005-02-10", "thesis_defense_date": "2005-01-31", "thesis_approved_date": "2005-02-14", "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": "Jenkins, David Matthew", "advisor_list": "Peters, Jonas C.", "comittee_list": "Gray, Harry B.; MacMillan, David W. 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"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/16564" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/16564" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/16564" } ] } } ], "eprint_status": "archive", "userid": 2, "dir": "disk0/00/00/23/49", "datestamp": "2004-06-01", "lastmod": "2023-11-08 00:44:06", "status_changed": "2009-09-25 02:35:17", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "jcthomas@alum.mit.edu", "id": "Thomas-John-Christopher", "name": { "family": "Thomas", "given": "John Christopher" }, "show_email": "NO" } ] }, "title": "Ligand Design, Coordination Chemistry, and Mechanistic Studies of (Phosphino)Borates and their Platinum, Nickel, and Copper Complexes", "ispublished": "unpub", "full_text_status": "public", "keywords": "boron; phosphorus; X-ray diffraction", "abstract": "Synthetic methods are presented for the preparation of various substituted bis(phosphino)borates. A relatively general protocol based on the delivery of a nucleophilic phosphine-containing carbanion to a borane electrophile has been developed. Preparative methods for the synthesis of substituted diarylchloroboranes from dimethyldiaryltin reagents provide the borane electrophiles. Methyldialkyl- or methyldiarylphosphines are selectively deprotonated at the phosphine-methyl using alkyl lithium bases to form the carbanion nucleophiles. The reaction of diverse phosphine-containing carbanions with diarylchloroboranes results in bis(phosphino)borates selectively substituted at the borate, at the phosphine, or at both positions. In addition to the generated lithium salts of the bis(phosphino)borates, cation-exchange protocols provide methods for preparing ammonium and thallium bis(phosphino)borate salts. Structural data for some of these derivatives are presented.
\r\n\r\nThe electronic properties of transition metals coordinated by bis(phosphino)borates are explored through NMR and IR spectroscopies. The spectroscopic features of platinum(II) dimethyl and methyl carbonyl complexes are examined for trends based on the substitution pattern of the (phosphino)borate ligand. These trends indicate that phosphine substituents have a more significant impact than borate substituents on electronics of the metal center. Structural and spectroscopic comparisons of structurally similar platinum(II) dimethyl and methyl carbonyl complexes indicate that the anionic bis(phosphino)borate ligand renders platinum(II) more electron-rich than structurally similar neutral phosphine donors. Related spectroscopic studies of anionic and neutral molybdenum(0) tetracarbonyl complexes provide results analogous to those found when comparing neutral and cationic platinum(II) systems.
\r\n\r\nComparative studies on the ligand exchange and benzene C-H activation chemistry of structurally similar platinum(II) complexes convey the similarities and differences between zwitterionic and cationic systems. Examination of THF ligand self-exchange by magnetization transfer shows a change in mechanism between the neutral and cationic species. Both bis(phosphino)borate-ligated and neutral bis(phosphine) platinum methyl solvento complexes undergo a benzene C-H activation to form the corresponding phenyl solvento complex; however, the rates of reaction and ultimate products differ. Extensive isotopic studies indicate that the zwitterionic system forms observable intermediates prior to benzene C-H activation, some of which are attributable to ligand metalation processes.
\r\n\r\nStructural and spectroscopic studies of a phenyl-substituted tris(phosphino)borate on platinum are presented. Alkyl- and hydride-containing platinum(II) and platinum(IV) species have been synthesized. The structural and spectroscopic features of these complexes are compared to related tris(pyrazolyl)borate systems on platinum.
\r\n\r\nCoordination and reaction chemistry of an isopropyl-substituted tris(phosphino)borate on nickel are discussed. Complexes in the Ni(II), Ni(I), and Ni(0) oxidation states have been prepared. This system is compared through structural, spectroscopic, and electrochemical methods to related phenyl-substituted tris(phosphino)borate chemistry on nickel. Reactivity studies aimed at preparing Ni(III) and Ni(IV) complexes containing metal-ligand multiple bonds through group-transfer reactions are presented. Theoretical studies using density functional methods are used to probe several target species containing multiply-bonded ligands.
\r\n\r\nThe coordination chemistry of copper(I) is explored using bis(phosphino)borates. Both aryl- and alkyl-substituted bis(phosphino)borates provide access to copper(I) complexes. A tert-butyl-substituted bis(phosphino)borate is particularly useful for preparing a family of three-coordinate compounds. The spectroscopic and structural features of these complexes are compared with similar, previously described examples.
", "date": "2004", "date_type": "degree", "id_number": "CaltechETD:etd-06012004-115510", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechETD:etd-06012004-115510", "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": "2004-06-01", "doi": "10.7907/GCAQ-8D59", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "jeb@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": "jkbarton@caltech.edu", "id": "Barton-J-K", "name": { "family": "Barton", "given": "Jacqueline K." }, "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": "2004-06-01", "thesis_defense_date": "2004-05-28", "thesis_approved_date": "2004-06-01", "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": "2004", "author_list": "Thomas, John Christopher", "advisor_list": "Peters, Jonas C.", "comittee_list": "Bercaw, John E.; Stoltz, Brian M.; et el." } ]