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"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/106291" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/106291" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/106291" } ] } } ], "eprint_status": "archive", "userid": 50, "dir": "disk0/00/00/75/14", "datestamp": "2013-03-13 21:42:31", "lastmod": "2020-02-12 02:07:25", "status_changed": "2013-03-13 21:42:31", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Treco-Brian-G-R-T", "name": { "family": "Treco", "given": "Brian G. R. T." }, "show_email": "NO" } ] }, "title": "Production of Transition Metal Oxidants through Design and Synthesis of Polyanionic Chelating Ligands", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "
Ligand design criteria for stabilization of high valent metals have been developed\r\nand applied to osmium, copper, and cobalt. Ligands have been designed to have\r\nfavorable coordination properities, be noninnocent, and be resistant to oxidative\r\ndegradation.
\r\n\r\nA new subset of ligands has been synthesized, these being called Class II polyanionic\r\nchelating (PAC) ligands. These ligands possess two N-amido donors and two\r\nalkoxy donors. Both units have pKa's of approximately 18 and so would be expected\r\nto be very powerful donors. A number of ligands of this type have been developed\r\nwith 5,5,5; 5,6,5; 6,5,6; and 6,6,6 coordination geometries. The key steps in all of\r\nthe syntheses are coupling of highly hindered carboxylic acids with highly hindered\r\ndiamines.
\r\n\r\nIt is found that the 5,5,5; 5,6,5; and 6,5,6 coordinating ligands all stabilize\r\nOs(VI) monooxo compounds. The 5,6,5 and 6,5,6 coordinating ligands also stabilize\r\nOs(IV) complexes of octahedral geometry. The 6,6,6 ligands of this type do not\r\ncoordinate to osmium. Of the 5,6,5 ligands, the most interesting results have been\r\nobtained with H\u2084HMPA-DMP, or 2,4-bis-hydroxymethylpropamido-2,4-dimethyl-\r\n3-pentanone. Reaction of this with potassium osmate produces Os(VI)(\u03b7\u2074-HMPA-DMP)O. This molecule has been structurally characterized. It assumes a distorted\r\nsquare pyramidal geometry with the metal atom 0.8 \u00c5 above the plane formed by\r\nthe four donor atoms of the PAC ligand. The distortion appears to occur by pyramidalization\r\nat the amide nitrogen atoms, as is shown by the \u03c7N values (17.0\u00b0\r\nand 9.1\u00b0). Os(HMPA-DMP)O undergoes a number of interesting reactions. It is\r\ncleanly converted to the trans-K\u2082Os(\u03b7\u2074-HMPA-DMP)O\u2082 species with base; it can be\r\nelectrochemically reduced to a stable (although highly air-sensitive) Os(V) species;\r\nand it can be chemically reduced to produce trans-Os(IV)(\u03b7\u2074-HMPA-DMP)L\u2082 complexes\r\nwhere L can be a wide variety of pyridines. These Os(IV) compounds may\r\nbe oxidized chemically or electrochemically to produce Os(V) compounds. The\r\nOs(V)/(IV) potential may be precisely controlled by appropriate choices of L allowing\r\nproduction of tunable oxidants. It is also observed that these Os(IV) compounds\r\nreact with molecular oxygen to regenerate the Os(VI) monooxo species. The compounds\r\ncatalytically reduce molecular oxygen and oxidize triphenylphosphine to\r\ntriphenylphosphine oxide. Kinetic studies are consistent with a rate-determining\r\nstep involving dissociation of a pyridine ligand from the trans-Os(IV)(\u03b7\u2074-HMPA-DMP)\r\nL\u2082 species to generate a vacant coordination site to which oxygen may bind.\r\nThe reaction has been examined with a variety of pyridine ligands. The rate of\r\nair oxidation decreases with increased electron donor ability of substituents on the pyridine ring, kobs being 1.9(1) X 10\u207b\u2076 min\u207b\u00b9 for the compound synthesized from\r\n4-bromopyridine and kobs for compounds synthesized with dialkylaminopyridines being\r\nvirtually too small to measure. Similar Os(VI) monooxo and octahedral Os(IV)\r\ncompounds have been synthesized with a number of other Class II PAC ligands.\r\nThe Os(IV) and Os(VI) compounds produced in this work have been compared to\r\nsimilar species produced with Class I PAC ligands.
\r\n\r\nThe Class II PAC ligands have also been used to stabilize trivalent copper.\r\nA number of such compounds have been synthesized (one of which, [TPP][Cu(\u03b7\u2074\r\n-HMPA-B)]) has been structurally characterized) and compared with the corresponding\r\nClass I compounds. While no Cu(III)-Class I PAC complexes were stable (although\r\nreversible Cu(III) /(II) were observed in these cases), the Class II PAC ligands\r\nled to stable Cu(III) complexes, exhibiting Cu(III) /(II) potentials as low as -1.06 V\r\nvs Fe\u207a /Fe. Such potentials are much lower than have been seen for any complexes\r\nsynthesized to date with first-row donor atoms. The [TMA][Cu(III)(HMPA-DMP)]\r\ncomplex is an example of a Cu(III) compound with a completely innocent ligand\r\ncomplement. In this case, resonance structures from lower oxidation states are not\r\npossible thus enabling the oxidation state in this complex to be unambiguously\r\nassigned as +III.
\r\n\r\nThe Class II PAC ligands stabilize cobalt in the rare trivalent, square planar\r\nform. These compounds, while paramagnetic with two unpaired spins, may be\r\ncharacterized by proton NMR. One such complex, Na[Co(III)(HMPA-B)] has been\r\ncharacterized by X-ray crystallography. These compounds catalyze the epoxidation\r\nof styrene using iodosoarenes as the stoichiometric oxidants.
\r\n", "date": "1988", "date_type": "degree", "id_number": "CaltechTHESIS:03132013-111018743", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:03132013-111018743", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Tony Diaz", "deposited_on": "2013-03-13 21:42:31", "doi": "10.7907/R8X9-3306", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Collins-T-J", "name": { "family": "Collins", "given": "Terrence J." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "chair" }, { "id": "Collins-T-J", "name": { "family": "Collins", "given": "Terrence J." }, "role": "member" }, { "email": "chans@its.caltech.edu", "id": "Chan-S-I", "name": { "family": "Chan", "given": "Sunney I." }, "role": "member" }, { "email": "jlbchamp@caltech.edu", "id": "Beauchamp-J-L", "name": { "family": "Beauchamp", "given": "Jesse L." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1987-07-17", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1988", "author_list": "Treco, Brian G. R. T.", "advisor_list": "Collins, Terrence J.", "comittee_list": "Gray, Harry B.; Collins, Terrence J.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/5562", "eprint_id": 5562, "rev_number": 28, "documents": [ { "id": "/id/document/9451", "doc_id": 9451, "rev_number": 5, "files": [ { "id": "/id/file/59474", "fileid": 59474, "datasetid": "document", "objectid": 9451, "filename": "Keech_jt_1987.pdf", "mime_type": "application/pdf", "filesize": 7664489, "mtime": "2012-12-26 03:21:55", "url": "/5562/1/Keech_jt_1987.pdf" } ], "eprint_id": 5562, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": "Keech_jt_1987.pdf", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "final", "relation": { "items": [ { "type": "http://eprints.org/relation/hasVolatileVersion", "uri": "/id/document/25430" }, { "type": "http://eprints.org/relation/haspreviewThumbnailVersion", "uri": "/id/document/25430" }, { "type": "http://eprints.org/relation/hasVersion", "uri": "/id/document/25430" } ] } }, { "id": "/id/document/9459", "doc_id": 9459, "rev_number": 3, "files": [ { "id": "/id/file/205150", "fileid": 205150, "datasetid": "document", "objectid": 9459, "filename": "Keech_Permission.txt", "mime_type": "text/plain", "filesize": 1913, "mtime": "2016-08-22 21:18:44", "url": "/5562/2/Keech_Permission.txt" } ], "eprint_id": 5562, "pos": 2, "format": "text/plain", "format_desc": "author ok 2010", "language": "en", "security": "internal", "license": "other", "main": "Keech_Permission.txt", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "release" }, { "id": "/id/document/25430", "doc_id": 25430, "rev_number": 2, "files": [ { "id": "/id/file/59472", "fileid": 59472, "datasetid": "document", "objectid": 25430, "filename": "preview.png", "mime_type": "image/png", "hash": "30091fd05b6c9100ef39a9e67cae44fb", "hash_type": "MD5", "filesize": 11544, "mtime": "2012-12-26 03:21:55", "url": "/5562/4/preview.png" } ], "eprint_id": 5562, "pos": 4, "placement": 4, "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/9451" }, { "type": "http://eprints.org/relation/ispreviewThumbnailVersionOf", "uri": "/id/document/9451" }, { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/9451" } ] } }, { "id": "/id/document/102079", "doc_id": 102079, "rev_number": 3, "files": [ { "id": "/id/file/293815", "fileid": 293815, "datasetid": "document", "objectid": 102079, "filename": "Keech_jt_1987.zip", "mime_type": "application/x-zip", "hash": "caa146cf3a38084651eb62c70c733b94", "hash_type": "MD5", "filesize": 15743124, "mtime": "2019-06-28 16:40:26", "url": "/5562/5/Keech_jt_1987.zip" } ], "eprint_id": 5562, "pos": 5, "placement": 5, "mime_type": "application/x-zip", "format": "application/zip", "format_desc": "TIFFs", "language": "en", "security": "internal", "license": "other", "main": "Keech_jt_1987.zip", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "archival" }, { "id": "/id/document/125576", "doc_id": 125576, "rev_number": 1, "files": [ { "id": "/id/file/371010", "fileid": 371010, "datasetid": "document", "objectid": 125576, "filename": "indexcodes.txt", "mime_type": "text/plain", "hash": "0a8d51c7b6480a6d377b509a97d4007e", "hash_type": "MD5", "filesize": 905, "mtime": "2021-06-24 00:15:25", "url": "/5562/6/indexcodes.txt" } ], "eprint_id": 5562, "pos": 6, "placement": 6, "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/9459" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/9459" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/9459" } ] } } ], "eprint_status": "archive", "userid": 51, "dir": "disk0/00/00/55/62", "datestamp": "2010-02-26 23:58:48", "lastmod": "2019-12-21 03:58:46", "status_changed": "2010-02-26 23:58:48", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "john.keech@kodak.com", "id": "Keech-John-Tyler", "name": { "family": "Keech", "given": "John Tyler" }, "show_email": "NO" } ] }, "title": "High Valent Osmium Complexes Incorporating a Tetradentate Tetraanionic Chelating Ligand; Stabilization Modification Resulting from the Formation of Non-Planar Amides", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "A new tetradentate tetraanionic chelating ligand has been synthesized: 1,2-bis(3,5-dichloro-2-hydroxybenzamido)-4,5-dichlorobenzene, H4CHBA-DCB. This ligand is one of a class of polyanionic chelating (PAC) ligands synthesized by the Collins group for stabilizing high valent metal centers. H4CHBA-DCB has an aromatic framework that is chlorinated for added chemical resistance. Reacting equimolar amounts of H4CHBA-DCB and K2[Os(OH)4(O)2] coordinates the ligand as trans-K2[Os(\u03b74-CHBA-DCB)(O)2], 3. Compound 3 undergoes reversible protonation at an oxo ligand to produce trans-K[Os(\u03b74-CHBA-DCB)(O)(OH)], 4. Compound 4 reacts with solid MgSO4 and forms the square-pyramidal mono-oxo complex Os(\u03b74-CHBA-DCB)(O), 5. Most oxidizing agents, with the exception of bromine, decompose 3 into a black amorphous material. Bromination of 3 produces a compound similar to 4 and is proposed to be trans-K[Os(\u03b74-CHBA-DCB)(O)(OBr)], 6. Triphenylphosphine readily reduces Os(VI)3 to a neutral Os(IV) complex, trans-Os(\u03b74-CHBA-DCB)(PPh3)2, 7. The ancillary phosphine ligands of 7 prove to be substitutionally labile and can be exchanged for other Lewis bases (e.g., py, t-Bupy, bipy, dppe, and t-BuNC) to produce a series of Os(IV) complexes. Using cyclic voltammetry, the formal potentials of the Os(V/IV), Os(IV/III), and Os(III/II) couples are determined in CH2Cl2. In liquid SO2, the formal potentials of the Os(V/IV), Os(2+/+), and Os(3+/2+) couples are measured for three compounds, the highest potential being at +1.70 V vs. Fc+/Fc or ca. +2.4 V vs. NHE. A fourth irreversible couple is observed at +2.12 to +2.20 V vs. Fc+/Fc. These osmium complexes display temperature-independent paramagnetism.
\r\n\r\nOs(IV) complexes with bidentate ligands (e.g., bipy and dppe) and Lewis acid ligands (t-BuNC) form cis complexes where the (\u03b74-CHBA-DCB)4- ligand is non-planar, and the auxiliary ligands are cis to one another. Two such complexes have been crystallographically characterized: cis-\u03b2-Os(\u03b74-CHBA-DCB)(bipy), 11, and cis-\u03b1-Os(\u03b74-CHBA-DCB)(PPh3)(t-BuNC), 14. Compound 11 crystallizes with 0.5 equiv EtOH solvate in the triclinic space group P1̅ with a = 10.860(3) \u00c5, b = 12.633(3) \u00c5, c = 12.844(4) \u00c5, \u03b1 = 117.42(2)\u00b0, \u03b2 = 90.42(3)\u00b0, \u03b3 = 95.90(3)\u00b0, V = 1552.2(7) \u00c53, Z = 2, Dcalc = 1.97 g/cm3, and Rf = 0.047 (I > 0; 2888 reflections). Compound 14 crystallizes in the orthorhombic space group Pbca with a = 22.09(2) \u00c5, b = 19.92(2) \u00c5, c = 19.40(2) \u00c5, V = 8537(4) \u00c53, Z = 8, Dcalc = 1.69 g/cm3, and Rf = 0.063 (I > 0; 1564 reflections). These structures contain novel non-planar amide groups. The amount of deformation in each amide is quantified by a torsion angle analysis. Two bonding changes cause the amide non-planarity: amide C-N bond rotation and pyramidalization of the amide nitrogen atom. Consistent with the presence of non-planar amides, unusually high amide carbonyl stretching frequencies are observed (1650-1695 cm-1), which imply that amide delocalization stabilization has been restricted.
\r\n\r\nThe cis-\u03b1 and trans isomers of [Os(\u03b74-CHBA-DCB)(t-Bupy)2]+ are in equilibrium with one another. From the measured equilibrium constant of 1.3 (in favor of the trans) and the formal reduction potentials for each isomer, the equilibrium constants for the interconversion of the neutral (3.4 x 103), anionic (2.4 x 1011), and dianionic (2.0 x 1015) species are derived. The trend in equilibrium constants shows that the cis-\u03b1 ligand set is increasingly favored as the metal is oxidized. A linear free energy relationship (LFER) is established between the cis-\u03b1 ⇆ trans equilibrium constants of Os(\u03b74-CHBA-DCB)(p-X-py)2 [X = MeO, t-Bu, Et, Me, H, Br, Cl, Ac] and both Fischer \u03c3̅ (\u03c1 = -2.10, r = 0.948) and Hammett \u03c3p (\u03c1 = -1.60, r = 0.949) substituent parameters. The formal potentials of the Os(V/IV), (IV/III), and Os(III/II) couples of both the cis-\u03b1 and trans isomers also correlate with \u03c3̅ constants, showing that the electron density at the metal center is perturbed in a predictable manner by the pyridine substituents. These LFERs show that the isomerization equilibria are controlled by electronic demand for stabilization at the metal center with the cis-\u03b1 ligand set being more electron-donating than the trans set. This difference apparently results from the increased localization of the amide nitrogen lone pair due to restricted amide delocalization in the non-planar amide groups of the cis-\u03b1 isomers. The localized lone pair probably enhances \u03c3- and \u03c0-bonding between the amide nitrogen atoms and the osmium center. The balance between the stabilization derived from the cis-\u03b1 isomer and the destabilization incurred from restricted amide delocalization may determine which isomer is thermodynamically most stable.
\r\n\r\nThe mechanism for the interconversion of cis-\u03b1 and trans isomers is probed through kinetic rate measurements and ligand exchange studies. Most of the results suggest that an intramolecular \"twist\" mechanism, T, requiring no ligand dissociation steps, controls the isomerization processes. The mechanism explains why no cis-\u03b2 isomers are detected during the isomerization of cis-\u03b1 and trans isomers. The activation parameters are derived for the cis-\u03b1 \u2192 trans isomerizations of three systems: Os(\u03b74-CHBA-DCB)(t-Bupy)2 (\u0394H\u2260 = 21.6(19) kcal/mol; \u0394S\u2260 = -10(6) eu), Os(\u03b74-CHBA-DCB)(O =PPh3)2 (\u0394H\u2260 = 21.6(2) kcal/mol; \u0394S\u2260 = 0.3(6) eu), and [Os(\u03b74-CHBA-DCB)(O =PPh3)2]+ (\u0394H\u2260 = 23.7(6) kcal/mol; \u0394S\u2260 = + 17(2) eu). This suggests that the different rates of isomerization result from entropic differences in the transition state, not enthalpic differences. That is, the t-Bupy system has the \"tightest\" transition state, as evidenced by the most negative \u0394S\u2260, and consequently the slowest isomerization rate. The rates are observed to be faster in the d3 Os(V) phosphine oxide system than in its d4 Os(IV) analog.
", "date": "1987", "date_type": "degree", "id_number": "CaltechTHESIS:02262010-145408928", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:02262010-145408928", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Standard Oil of Ohio (SOHIO)" }, { "agency": "W. R. Grace" }, { "agency": "Shell Oil Company" } ] }, "collection": "CaltechTHESIS", "reviewer": "Gayle Hammer", "deposited_by": "Tony Diaz", "deposited_on": "2010-02-26 23:58:48", "doi": "10.7907/A4N9-5E16", "alt_title": { "items": [ "Stabilization Modification Resulting from the Formation of Non-Planar Amides" ] }, "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Collins-T-J", "name": { "family": "Collins", "given": "Terrence J." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "id": "Collins-T-J", "name": { "family": "Collins", "given": "Terrence J." }, "role": "chair" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1986-08-08", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. 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"http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/103698" } ] } } ], "eprint_status": "archive", "userid": 8820, "dir": "disk0/00/01/18/47", "datestamp": "2019-10-23 17:28:25", "lastmod": "2021-04-16 22:59:27", "status_changed": "2019-10-23 17:28:25", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Peake-Geoffrey-Tower", "name": { "family": "Peake", "given": "Geoffrey Tower" }, "show_email": "NO" } ] }, "title": "Studies of the Donor Properties of New Polyanionic Chelating Ligands through the Synthesis and Characterization of Osmium Complexes", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "The synthesis, characterization, physical and chemical properties of osmium complexes containing highly donating polyanionic chelating (PAC) ligands are discussed.
\r\n\r\nThe tetradentate tetraanionic ligand HBA-B (H4HBA-B \u2261 1,2-bis(2-hydroxybenzamido)benzene) coordinates to osmium to form a variety of complexes. Reaction of H4HBA-B with K2[Os(OH)4(O)2] gives an osmium(VI) trans-dioxo complex coordinating the PAC ligand through two deprotonated phenol groups and two deprotonated amide groups. Reduction of the dioxo species with triphenylphosphine gives the neutral osmium(IV) species trans-Os(\u03b74-HBA-B)(PPh3)2 (3). This complex is an excellent starting material to make a series of osmium(IV) complexes because of the lability of the phosphine ligands. Ligand exchange reactions with nitrogen-base ligands, anionic two-electron donor ligands, mono- and bidentate phosphines, \u03c0-acid ligands, and bipyridines are observed. Most of the osmium(IV) PAC ligand complexes prepared are paramagnetic with \u03bceff ~1 BM. The paramagnetic osmium(IV) species all exhibit well-resolved, paramagnetically shifted NMR spectra. The complex trans-Os(\u03b74-HBA-B)(PPh3)(py) (5) has twelve inequivalent sets of protons, all of which are on aromatic rings. The twelve resonances are observed in the 1H NMR spectrum in the range +11 to -5 ppm. The results of 2D-COSY and difference NOE experiments allow the complete assignment of the 1H NMR spectrum.
\r\n\r\nElectrochemical studies of these osmium(IV) complexes, and the coordination chemistry observed indicate that these PAC ligands are very good electron donors to osmium. The Os(IV/III) reversible couples for the neutral osmium(IV) species have potentials m the range -0.9 to -0.7 V vs. Fc+/Fc. The cation/neutral reversible couples have potentials in the range +0.2 to +0.35 V vs. Fc+/Fc, but probably cannot be called Os(V/IV) couples. Reaction of 3 with carbon monoxide produces a rare osmium(IV) carbonyl complex, cis-\u03b1-Os(\u03b74-HBA-B)(PPh3)(CO) (10). Reaction of t-butylisocyanide with 3 gives the analogous mono-phosphine mono-isocyanide. The stability of these complexes in an indication of the strong donating nature of the PAC ligand.
\r\n\r\nA crystal structure of 10 shows it to have a cis-\u03b1 coordination geometry. Complexes with cis geometries can also be made by reacting 3 with bidentate ligands, such as dppe. Cis-\u03b1 and cis-\u03b2 osmium complexes of the HBA-B PAC ligand, and other PAC ligand complexes, contain the first nonplanar amide ligands. We have defined three causes for the formation of nonplanar amide ligands: (1) structural requirements of the metal center (for instance coordination of a bidentate dppe ligand forcing a cis geometry), (2) depletion of electron density from the metal center (either by oxidation or coordination of an electron withdrawing ligand), causing the amide ligands to adopt the more highly donating nonplanar structure and offset the depletion of electron density at the metal, (3) steric interactions forcing deformation of the amide ligand to a nonplanar state.
\r\n\r\nThe syntheses of osmium complexes containing the CHBA ligand (H2CHBA \u2261 3,5-dichloro-2-hydroxybenzamide) are discussed. Several complexes, including trans-Os(\u03b72-CHBA)2(PBu3)2 (26) and trans-Os(\u03b72-CHBA)2(OPBu3)2 (27), have been prepared in attempts to make a long-lived catalyst for the electrochemical oxidation of alcohols. The cyclic voltammetric experiments with 26 and 27 in the presence of alcohol are discussed. It appears that 27 exhibits catalytic behavior and 26 does not. A detailed study probing the catalysis has not been done.
\r\n\r\nThe results of reactions between K2[Os(OH)4(O)2] and ligands similar to 2-(2-hydroxyphenyl)imidazole are reported. The reactions give neutral osmium(VI) trans-dioxo complexes containing two 2-(2-phenoxy)imidazole ligands coordinated as bidentate monoanions through a phenoxy ligand and an imidazole ligand. This coordination mode contrasts with that observed for osmium complexes of 2-(3,5-dichloro-2-hydroxyphenyl)-5,6-dichlorobenzimidazole, which coordinates as a dianion.
", "date": "1987", "date_type": "degree", "id_number": "CaltechTHESIS:10232019-094659896", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:10232019-094659896", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Melissa Ray", "deposited_by": "Mel Ray", "deposited_on": "2019-10-23 17:28:25", "doi": "10.7907/68mt-5y71", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Collins-T-J", "name": { "family": "Collins", "given": "Terrence J." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "chair" }, { "id": "Collins-T-J", "name": { "family": "Collins", "given": "Terrence J." }, "role": "member" }, { "email": "rhg@caltech.edu", "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "role": "member" }, { "email": "chans@its.caltech.edu", "id": "Chan-S-I", "name": { "family": "Chan", "given": "Sunney I." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1986-11-24", "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": "1987", "author_list": "Peake, Geoffrey Tower", "advisor_list": "Collins, Terrence J.", "comittee_list": "Gray, Harry B.; Collins, Terrence J.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/11346", "eprint_id": 11346, "rev_number": 20, "documents": [ { "id": "/id/document/96259", "doc_id": 96259, "rev_number": 4, "files": [ { "id": "/id/file/275399", "fileid": 275399, "datasetid": "document", "objectid": 96259, "filename": "Spies_GH_1985.pdf", "mime_type": "application/pdf", "hash": "7be4fb8ace991afef5dba978f799f507", "hash_type": "MD5", "filesize": 81270769, "mtime": "2019-01-18 19:02:22", "url": "/11346/1/Spies_GH_1985.pdf" } ], "eprint_id": 11346, "pos": 1, "placement": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": 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"/id/document/96259" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/96259" } ] } } ], "eprint_status": "archive", "userid": 11566, "dir": "disk0/00/01/13/46", "datestamp": "2019-01-18 20:11:58", "lastmod": "2021-04-19 22:33:09", "status_changed": "2019-01-18 20:11:58", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Spies-George-Harlan", "name": { "family": "Spies", "given": "George Harlan" }, "show_email": "NO" } ] }, "title": "I. Studies on the Coordination of Bis-hydroxybenzamido Chelating Ligations to Chromium, Iron, and Osmium. II. A Survey of the Organometallic Chemistry of Osmium Tetraoxide", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "The coordination chemistry of chromium, iron, and osmium with bis-hydroxybenzamido chelating ligands was investigated. Two types of complexes were obtained on reacting CrCl3 \u2022 6H2O with 1,2-bis(3,5-dichloro-2-hydroxybenzanido)-ethane ((H)4CHBA-Et). A neutral dimeric complex, in which two chelates bridge two metal centers, was discovered and characterized by X-ray crystallography. This is the first molecule in which both forms of monodentate organic amide coordination (i.e., O-bound and N-bound coordination) have been found. The N-bound amide was shown to be a better \u03c3-donor. This is the first well-characterized example of N-coordination to chromium(III).
\r\n\r\nA second complex, which is a precursor to the neutral dimer, has not been fully characterized. It may also be dimeric. Similar complexes, with different bis-hydroxybenzamido ligands, have been examined. Iron(III) species, synthesized from these ligands and FeCl3, appear to be analogous to the latter chromium(III) compounds.
\r\n\r\nX-ray crystallographic studies have complemented investigations into the coordination chemistry of these bis-hydroxybenzamido ligands with several transition metals. In addition to the dimeric chromium(III) complex, in which the ligand bridges two metal centers, many osmium(IV) complexes were found with the bis-hydroxybenzamido ligands coordinated to one metal center as a planar tetradentate tetraanion. These structures exhibited the first examples of bonds between osmium(IV) and an N-coordinated organic amide ligand and a phenoxide ligand. One such complex, a \u00b5-oxo dimer, was found with potassium ions in unusually low coordination environments (i.e., four- and five-coordinate). Oxidation of trans-Os( CHBA-Et)(py)2 subsequently resulted in crystals of a new con1plex with a hydroxy and a methoxy group on the ethylene unit bridging the amide nitrogen atoms of the chelated ligand. The bond distances and angles for this molecule are very similar to those of its precursor, trans-Os(CHBA-Et)(py)2. The ligand, (H)4 CHBA-Et, was found to cocrystallize with pyridinium chloride. This structure has provided a benchmark for comparison with complexed chelates; few significant differences were observed.
\r\n\r\nThe fusion of 2,3-bis(2-hydroxy-benzamido)-2,3-butane with (NH4)2OsCl6 (T > 300\u00b0C) resulted in the formation of an osmium(IV)-imidazoline complex.
\r\n\r\nAlso examined was the organometallic chemistry of osmium tetraoxide. Oxidation of low valent carbonyl complexes with the quinuclidine adduct of osmium tetraoxide resulted in attack of both the low valent metal and a carbonyl ligand with the formation of \u00b5-CO2 mixed-valent complexes. The surprising stability of this new type of CO2 complex is kinetic in origin as den1onstrated by the chemistry of a series of compounds. Decomposition with loss of CO2 was observed for more labile metal complexes. In the absence of nitrogenous bases, oxidation of Ru(CO)3(PPh3)2 with osmium tetraoxide resulted in the formation of what is believed to be a tetranuclear complex. The low valent metal center and a coordinated carbonyl ligand were oxidized.
\r\n\r\nOne other mode of reactivity was discovered. Oxidative addition of osmium tetraoxide to Pt(PPh3)2(C2H4) displaced the ethylene ligand with the formation of a \u00b5-oxo bridged tetranuclear complex. These and other potential modes of OsO4 reactivity with organometallic and inorganic complexes are discussed.
", "date": "1985", "date_type": "degree", "id_number": "CaltechTHESIS:01182019-103133548", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:01182019-103133548", "related_url": { "items": [ { "description": "Publications from Appendix D.", "type": "doi", "url": "https://doi.org/10.1021/ja00389a093" }, { "description": "Publications from Appendix D.", "type": "doi", "url": "https://doi.org/10.1039/c39830000681" }, { "description": "Publications from Appendix D.", "type": "doi", "url": "https://doi.org/10.1039/c39840000198" }, { "description": "Publications from Appendix D.", "type": "doi", "url": "https://doi.org/10.1021/ja00328a028" } ] }, "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Melissa Ray", "deposited_on": "2019-01-18 20:11:58", "doi": "10.7907/s19j-2033", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "advisor" }, { "id": "Collins-T-J", "name": { "family": "Collins", "given": "Terrence J." }, "role": "co-advisor" } ] }, "thesis_committee": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "chair" }, { "id": "Collins-T-J", "name": { "family": "Collins", "given": "Terrence J." }, "role": "member" }, { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "member" }, { "email": "wag@caltech.edu", "id": "Goddard-W-A-III", "name": { "family": "Goddard", "given": "William A., III" }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1984-10-04", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1985", "author_list": "Spies, George Harlan", "advisor_list": "Bercaw, John E. and Collins, Terrence J.", "comittee_list": "Bercaw, John E.; Collins, Terrence J.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/11240", "eprint_id": 11240, "rev_number": 17, "documents": [ { "id": "/id/document/94756", "doc_id": 94756, "rev_number": 4, "files": [ { "id": "/id/file/269340", "fileid": 269340, "datasetid": "document", "objectid": 94756, "filename": "Roddick_DM_1984.pdf", "mime_type": "application/pdf", "hash": "90e386258867d3507e805b06c284fe20", "hash_type": "MD5", "filesize": 47954581, "mtime": "2018-10-22 18:21:05", "url": "/11240/1/Roddick_DM_1984.pdf" } ], "eprint_id": 11240, "pos": 1, "placement": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": 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"type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/94756" } ] } } ], "eprint_status": "archive", "userid": 11566, "dir": "disk0/00/01/12/40", "datestamp": "2018-10-22 22:32:05", "lastmod": "2021-04-16 23:14:54", "status_changed": "2018-10-22 22:32:05", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Roddick-Dean-Michael", "name": { "family": "Roddick", "given": "Dean Michael" }, "show_email": "NO" } ] }, "title": "Synthesis, Structure, and Reactivity of Hydride and Phosphide Complexes of Hafnium and Zirconium", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "A series of alkyl hydride complexes Cp*2Hf(H)R (R=Et, CH2CHMe2, CH2CH2Ph; Cp* = \u03b7-C5Me5) have been prepared by reaction of Cp*2HfH2 with the appropriate olefin. The reactions of these compounds with H2 and C2H4 follow those of the previously reported zirconium isobutyl hydride, Cp*2Zr-(H)CH2CHMe2, giving Cp*2HfH2 and metallacyclopentane Cp*2Hf-CH2CH2CH2CH2, respectively, plus one equivalent alkane. All alkyl hydrides examined exhibit high thermal stability and decompose only slowly at 80\u00b0C. The thermolysis of Cp*2Hf(H)CH2CHMe2 yields a 1:1 mixture of Cp*2HfH2 and a metallacyclobutane complex Cp*2HfCH2CH(Me)CH2. A proposed mechanism for the formation of Cp*2HfCH2CH(Me)CH2 is given, involving initial \u03b3-H abstraction from the isobutyl methyls of Cp*2Hf(H)CH2CHMe2. Cp*2HfH2 also reacts cleanly with t-butylacetylene to form a remarkably stable alkenyl hydride complex, Cp*2Hf(H)CH=CHtBu. The reactivity of Cp*2Hf(H)CH=CHtBu with H2 and C2H4 is similar to that observed for the related alkyl hydrides. The hydride complexes Cp*2Hf(H)Ph and Cp*2Hf-(H)CH2CMe3 have been conveniently prepared by the metathesis of Cp*2HfH2 with PhLi and LiCH2CMe3, respectively.
\r\n\r\nCp*2HfH2 reacts cleanly with allene to form the \u03c0-allyl hydride Cp*2Hf(H)(\u03b73-CH2CHCH2). 1H and 13C NMR data as well as labeling studies indicate that Cp*2Hf(H)(\u03b73-CH2CHCH2) is highly fluxional, and isostructural to Cp*2Zr(H)(\u03b73-CH2CHCH2). The crystal structure of Cp*2Hf(H)(\u03b73-CH2CHCH2) is presented. The coordination of the allyl ligand is confirmed to be trihapto, with notably asymmetric Hf-C(allyl) distances (2.38, 2.48, 2.57 A). The final R index is 0.049. The hydride ligand has been reliably located, and represents the first structurally characterized example of a terminal Hf-H bond.
\r\n\r\nCp*2Zr(H)CH2CHMe2 has been shown to react cleanly with CO to form the enolate hydride Cp*2Zr(H)OCH=CHCHMe2. A proposed mechanism for formation of Cp*2Zr(H)OCH=CHCHMe2 involves hydride migration via the initially formed acyl hydride Cp*2Zr(H)(\u03b72-C(O)CH2CHMe2) to give a \u03c0-coordinated aldehyde complex Cp*2Zr(\u03b72-OCHCH2CHMe2), which subsequently \u03b2-H eliminates to give the observed product. Support for the intermediacy of a \u03c0-aldehyde complex in this transformation is provided by the reaction of Cp*2M(H)CH2CHMe2 (M=Zr, Hf) with excess CO under controlled conditions to give moderately stable \u03c0-aldehyde carbonyl complexes Cp*2M(CO)(\u03b72-OCHCH2CHMe2). Thermolysis of Cp*2Hf(CO)(\u03b72-OCHCH2CHMe2) results in a novel coupling reaction to form the enediolate Cp*2HfOC(CH2CHMe2)CHO. The coordinatively unsaturated zirconium \u03c0-aldehyde intermediate Cp*2Zr(\u03b72-OHCCH2-CHMe2) is also implicated in the reactions of acyl hydride Cp*2Zr(H)(\u03b72-C(O)CH2CHMe2) with trapping substrates C2H4, MeC\u2261CMe, H2, and HC\u2261CtBu upon warming to give Cp*2Zr(OCH(-CH2CHMe2)CH2CH2), Cp*2Zr(OCH(CH2CHMe2)C(Me)=C(Me)), Cp*2Zr-(H)OCH2CH2CHMe2, and Cp*2Zr(C\u2261CtBu)OCH2CH2CHMe2, respectively. Carbonylation of the alkenyl hydride Cp*2Hf(H)CH=CHtBu did not yield an aldehyde complex, but rather the metallacycle Cp*2Hf(OHC=CHCH(tBu)). Mechanistic interpretations of these and related reactions are presented.
\r\n\r\nA series of mono-ring, terminal phosphide complexes of hafnium have been prepared. Reaction of Cp*HfCl3 with one equivalent or excess LiPtBu2 yields deeply-colored phosphide complexes Cp*HfCl2(PtBu2) and Cp*HfCl(PtBu2)2, respectively. Alkyl and aryl derivatives of Cp*HfCl2 (PtBu2), Cp*HfR(Y)(PtBu2) (R=Y=Me; Y=Cl, R-CH2CMe, CH2Ph, Ph), are prepared either by direct alkylation, or from the corresponding chloro-alkyls Cp*ClnR3-n. Cp*HfMe2(PtBu2) reacts slowly with H2 to form a highly insoluble methyl hydridophosphide dimer, [Cp*HfMe(\u00b5-H)(\u00b5-PtBu2)]2. The crystal structure of [Cp*HfMe(\u00b5-H)(\u00b5-PtBu2)]2 reveals a symmetric-bridged Hf2P2 core with Hf-P distances of 2.805, 2.807 A. The hydride ligands have been tentatively located and form an assymetric Hf2H2 bridge (Hf-H = 2.12, 2.33 A) orthogonal to the planar Hf2P2 moiety. The final R index is 0.066. Hydrogenolysis of alkyl derivatives Cp*HfClR(PtBu2) (R = CH2CMe3, CH2Ph) affords an analogous chlorothydridophosphide dimer, [Cp*HfCl(\u00b5-H)(\u00b5-Pt Bu2)]2. Treatment of Cp*HfCl(PtBu2)2 with H2 leads to rapid cleavage of Hf-P bonds and formation of [Cp*HfCl(\u00b5-H)(\u00b5-PtBu2]2. Cp*HfCl2(PtBu2) also reacts with H2, albeit slower, to give products derived from initially-formed Cp*HfCl2H.
\r\n\r\nThe relatively low Hf-P bond energy suggested by hydrogenolysis reactions in these systems is further indicated by the reaction of Cp*HfCl2(PtBu 2) with CO to form the CO-insertion product, Cp*HfCl2 (\u03b72-C(O)PtBu2). The crystal structure of Cp*HfCl2(\u03b72-C(O)PtBu2) exhibits dihapto carboxyphosphide functionality, with Hf-C = 2.203 and Hf-O = 2.117 A. The P-C(acyl) bond is 0.08 A shorter than P-C(alkyl) values, and suggests a significant P-\u03c0 interaction. This has been confirmed by variable temperature studies, which reveal a substantial (10.7 kcal/mol) barrier to rotation about the P-C(acyl) bond.
", "date": "1984", "date_type": "degree", "id_number": "CaltechTHESIS:10222018-111603289", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:10222018-111603289", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Melissa Ray", "deposited_on": "2018-10-22 22:32:05", "doi": "10.7907/wbgr-yd42", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Collins-T-J", "name": { "family": "Collins", "given": "Terrence J." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "chair" }, { "email": "chans@its.caltech.edu", "id": "Chan-S-I", "name": { "family": "Chan", "given": "Sunney I." }, "role": "member" }, { "email": "rhg@caltech.edu", "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "role": "member" }, { "id": "Collins-T-J", "name": { "family": "Collins", "given": "Terrence J." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1984-01-30", "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": "1984", "author_list": "Roddick, Dean Michael", "advisor_list": "Collins, Terrence J.", "comittee_list": "Bercaw, John E.; Chan, Sunney I.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/11245", "eprint_id": 11245, "rev_number": 18, "documents": [ { "id": "/id/document/94797", "doc_id": 94797, "rev_number": 4, "files": [ { "id": "/id/file/269526", "fileid": 269526, "datasetid": "document", "objectid": 94797, "filename": "Berry_DH_1984.pdf", "mime_type": "application/pdf", "hash": "8cb59b40e89c42dba7fdbe767e9d3337", "hash_type": "MD5", "filesize": 30668940, "mtime": "2018-10-24 18:23:36", "url": "/11245/1/Berry_DH_1984.pdf" } ], "eprint_id": 11245, "pos": 1, "placement": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", 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"type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/94797" } ] } } ], "eprint_status": "archive", "userid": 11566, "dir": "disk0/00/01/12/45", "datestamp": "2018-10-24 22:50:49", "lastmod": "2021-04-16 23:20:53", "status_changed": "2018-10-24 22:50:49", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Berry-Donald-Harry", "name": { "family": "Berry", "given": "Donald Harry" }, "show_email": "NO" } ] }, "title": "Studies of the Reactivity of Permethylzirconocene Complexes with Binuclear Transition Metal Carbonyl Compounds", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "The low valent permethylzirconocene complex {Cp*2ZrN2}2N2 (Cp*\u2261\u03b75-C5Me5) reacts with binuclear transition metal carbonyl compounds of the general formula Cp2M2(CO)x (Cp\u2261\u03b75-C5H5) to produce trinuclear complexes. Two major modes of reactivity are observed. Compounds with M-M bonds that are easily reduced such as (CpM(CO)3)2 (M = W, Mo) react with {Cp*2ZrN2}2N2 to produce trinuclear species in which two CpM(CO)3 anions are connected to a Cp*2Zr dication via \u00b52-(C-\u03b71; O-\u03b71) carbonyl bridges. The structure of the molybdenum complex has been determined by single crystal X-ray diffraction methods. These trinuclear complexes are also produced in the reaction of the Cp*2ZrRR'(R,R' = H,alkyl) with two equivalents of the hydride complexes CpM(CO)3H\u00b7 The dinuclear complexes Cp*2M(H)(CpMo(CO)3)(M = Zr, L = PMe3; M = Hf, L = CO) have been similarly prepared by treatment of the zirconium or hafnium dihydride with the corresponding molybdenum hydride. The trinuclear complexes react with HX (X = Cl, OH) to produce CpM(CO)3H and Cp*2ZrX2.
\r\n\r\nThe other mode of reactivity between {Cp*2ZrN2}2N2 and metal dimers is observed with (CpM(CO)2)2 (M = Fe, Ru). In these cases trinuclear complexes are produced in which two carbonyl ligands are reductively coupled yielding an O2C2 moiety bridging the three metals. This coupling is reversible and the Zr(II) intermediate can be trapped with CO or other metal dimers. The iron analog is also produced in the reaction of Cp*2ZrI2 with Na(CpFe(CO)2).
\r\n\r\nThe reaction of {Cp*2ZrN2}2N2 with the bridging methylene complex cis-Cp2Ru2(CO)3(CH2) does not result in carbonyl coupling, yielding instead what appears on the basis of spectroscopic data to be a \u03c0-complex between permethylzirconocene and cis-Cp2Ru2(CO)3(CH2) held together only by \u00b52-(C-\u03b71; C,O-\u03b72) bridging carbonyl ligands.
\r\n\r\nThe ruthenium carbonyl coupled product, Cp*2Zr(O2C2)Ru2Cp2(CO)2, reacts under H2 to produce the bridging zirconoxy carbene complex trans-Cp2Ru2(CO)3(C(H)OZr(H)Cp*2). This complex is fluxional on the 1H and 13C NMR timescales. \u0394G\u2021 for this process is 14.0(2) kcal\u00b7mol-1 at -4\u00b0C. The fluxionality is best explained by a process involving a terminal carbine intermediate. The carbene formation is reversible, and treatment with D2 results in label incorporation in both the hydride and carbene hydrogen positions. Reaction with CO produces Cp*2Zr(CO)2, (CpRu(CO)2)2 and presumably H2. Treatment with BF3 or HBF4 results in C-O scission and produces the bridging methylene complex Cp2Ru2(CO)3(CH2). Labeling studies indicate both methylene hydrogens originate on zirconium. This bridging methylene complex can be synthesized in 60% yield by treatment of (CpRu(CO)2)2 with LiBEt3H in toluene.
\r\n", "date": "1984", "date_type": "degree", "id_number": "CaltechTHESIS:10242018-111901394", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:10242018-111901394", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "deposited_on": "2018-10-24 22:50:49", "doi": "10.7907/yahb-n031", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Collins-T-J", "name": { "family": "Collins", "given": "Terrence J." }, "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": "jlbchamp@caltech.edu", "id": "Beauchamp-J-L", "name": { "family": "Beauchamp", "given": "Jesse L." }, "role": "member" }, { "id": "Collins-T-J", "name": { "family": "Collins", "given": "Terrence J." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1984-01-31", "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": "1984", "author_list": "Berry, Donald Harry", "advisor_list": "Collins, Terrence J.", "comittee_list": "Bercaw, John E.; Grubbs, Robert H.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/429", "eprint_id": 429, "rev_number": 18, "documents": [ { "id": "/id/document/654", "doc_id": 654, "rev_number": 3, "files": [ { "id": "/id/file/4122", "fileid": 4122, "datasetid": "document", "objectid": 654, "filename": "Nocera_dg_1984.pdf", "mime_type": "application/pdf", "filesize": 6477189, "mtime": "2012-12-26 02:29:46", "url": "/429/1/Nocera_dg_1984.pdf" } ], "eprint_id": 429, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "format_desc": "Original (no OCR) Nocera_dg_1984.pdf", "language": "en", "security": "internal", "license": "other", "main": "Nocera_dg_1984.pdf", 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"dir": "disk0/00/00/04/29", "datestamp": "2005-02-01", "lastmod": "2020-03-05 19:35:32", "status_changed": "2009-09-25 01:37:22", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "nocera@mit.edu", "id": "Nocera-Daniel-George", "name": { "family": "Nocera", "given": "Daniel George" }, "orcid": "0000-0001-5055-320X", "show_email": "NO" } ] }, "title": "Spectroscopy, Electrochemistry, and Photochemistry of Polynuclear Metal-Metal Bonded Complexes", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "The spectroscopic, electrochemical, and photochemical properties of two d4 metal polynuclear complex systems were investigated: the quadruple bond complex, Re2Cl82-, and the M6X142- halide cluster ions of molybdenum(II) and tungsten (II).
\r\n\r\nThe vibrationally structured luminescence spectrum of Re2Cl82- at 5 K has confirmed that emission arises from the \u03b4\u03b4* singlet state. Both Re2Cl82- and electronically excited Re2Cl82- (Re2Cl82-*) undergo facile one-electron oxidation and reduction reactions. Aromatic amines quench Re2Cl82-* luminescence and a Marcus analysis of the steady state quenching rate constants suggest that Re2Cl83-|D+ is formed in the quenching reaction and that the ion-pair decays rapidly by back electron transfer. The luminescence of Re2Cl82-* is also quenched by electron acceptors (TCNE and chloranil) in nonaqueous solutions, forming Re2Cl8- and reduced acceptor. The back electron transfer reactions are near the diffusion controlled limit. Electrochemical measurements suggested that photogenerated Re2Cl8- anion could be trapped by Cl- to produce Re2Cl92-, thereby circumventing the efficient back reaction. Irradiation (\u03bb > 600 nm) of nonaqueous solutions of Re2Cl82- and chloranil or TCNE in the presence of excess Cl- does, indeed, produce Re2Cl92- in quantitative yield. Photolysis reactions employing a quencher (e.g. 2,3-dichloro-5,6-dicyano-benzoquinone) possessing a redox couple with a potential greater than that of Re2Cl9-/2- (0.53 vs. SCE) yielded Re2Cl9- as a final product. Thus, a single low energy photon facilitates a two-electron oxidation of Re2Cl82-. Direct two-electron oxidation of Re2Cl82-* by chlorine atom transfer reagents such as PtCl62- to produce Re2Cl9- was also attempted. Irradiation (\u03bb > 590 nm) of dichloromethane solutions containing Re2Cl82- and PtCl62- quantitatively yield Re2Cl9-. Qualitative kinetic experiments measuring the wavelength dependence of the reaction rate suggest that the photochemical reaction proceeds by a free radical pathway involving the 3A2u ligand field excited state of PtCl62- and does not involve an atom transfer reaction mechanism. These experiments are not without their ambiguities, however, and further areas of research are discussed. The crystal structure analysis of NBu4Re2Br9 is also presented.
\r\n\r\nThe M6X142- (M=Mo,W; X=Cl,Br,I) ions are intensely luminescent in the solid state and solution and the photophysical properties of the six cluster ions are documented. These results in conjunction with those of the EPR spectra of the electrochemically generated M6X14- anions are discussed in terms of recent theoretical models for the electronic structure of the cluster ions. Electrochemical experiments were also conducted and showed the M6X142- cluster ions to undergo reversible single-electron oxidation reactions. For Mo6Cl142- a quasi-reversible one-electron reduction wave was observed in addition to its oxidation wave. The electrochemical and photophysical properties of Mo6Cl142- suggested electrogenerated chemiluminescent behavior of the cluster ion. Emission, characteristic of Mo6Cl142-*, is observed upon electrochemical generation of Mo6Cl14- and Mo6Cl143-.
\r\n", "date": "1984", "date_type": "degree", "id_number": "CaltechETD:etd-02012005-160716", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechETD:etd-02012005-160716", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Sun Company" } ] }, "collection": "CaltechTHESIS", "deposited_by": "Imported from ETD-db", "deposited_on": "2005-02-01", "doi": "10.7907/T14G-4N32", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Collins-T-J", "name": { "family": "Collins", "given": "Terrence J." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "fanson@caltech.edu", "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." }, "role": "chair" }, { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "member" }, { "id": "Janda-K-C", "name": { "family": "Janda", "given": "Kenneth C." }, "role": "member" }, { "id": "Collins-T-J", "name": { "family": "Collins", "given": "Terrence J." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_submitted_date": "2005-02-01", "thesis_defense_date": "1983-08-16", "thesis_approved_date": "2005-02-01", "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": "1984", "author_list": "Nocera, Daniel George", "advisor_list": "Collins, Terrence J.", "comittee_list": "Anson, Fred C.; Gray, Harry B.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/11122", "eprint_id": 11122, "rev_number": 19, "documents": [ { "id": "/id/document/93116", "doc_id": 93116, "rev_number": 5, "files": [ { "id": "/id/file/262737", "fileid": 262737, "datasetid": "document", "objectid": 93116, "filename": "Najdzionek_JS_1982.zip", "mime_type": "application/x-zip", "hash": "668f7166ef282102866a71c338beb1af", "hash_type": "MD5", "filesize": 174126933, "mtime": "2018-07-13 17:23:20", "url": "/11122/1/Najdzionek_JS_1982.zip" } ], "eprint_id": 11122, "pos": 1, "placement": 1, "mime_type": "application/x-zip", "format": "application/zip", "format_desc": "TIFFs", "language": "en", 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Cyclic voltammetric (CV), chronoamperometric (CA), polarographic (including D.C., normal and differential pulse) and bulk electrolytic experiments were performed and the results show that all of these Rh(I) phosphine complexes are reduced in a two-electron process.
\r\n\r\nCV and CA measurements were used to determine the heterogeneous electron transfer rate constants for Rh[(C6H5)2P(CH2)2P(C6H5)2]2. The values determined were 0.0092 and 0.0087 cm/sec, respectively, and the results are discussed in relation to the Butler-Volmer formulation of electrode kinetics.
\r\n\r\nFluorescence measurements were made on the above rhodium complexes for n = 1, 3 and 4 at room temperature and at 77 K. None emit under ambient conditions in solution but the compound containing ligands with a single methylene unit backbone emitted at 77 K with a lifetime of 20 microseconds. The UV-Visible spectrum of reduced Rh(DPP)+2, the most stable of the reduced complexes, displayed a very intense absorption at 450 nm which was assumed to be charge-transfer in origin.
\r\n\r\nThe two-electron reduction of Rh2(2,5-dimethyl-2,5-diisocyanohexane)2+4 produced a unique species in which a CN- ion has been lost resulting in the formation of a cyclohexylimine ligand which bridges the metal atoms through the imine function. The strain imposed on the TMB ligand backbone forces the rhodium atoms to have the strongest interaction of any of the Rh(Br)+4 compounds studied [Rh(l)-Rh(2) = 2.970(1)\u00c5]. Linear isocyanide carbon-nitrogen distances range from 1.153(9) to 1.175(9) \u00c5 while the imine carbon-nitrogen is extended slightly to 1.254(9) \u00c5.
", "date": "1982", "date_type": "degree", "id_number": "CaltechTHESIS:07132018-094917474", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:07132018-094917474", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Tony Diaz", "deposited_by": "Mel Ray", "deposited_on": "2018-07-13 20:06:42", "doi": "10.7907/pqye-xp04", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Collins-T-J", "name": { "family": "Collins", "given": "Terrence J." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "fanson@caltech.edu", "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." }, "role": "chair" }, { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "role": "member" }, { "id": "Janda-K-C", "name": { "family": "Janda", "given": "Kenneth C." }, "role": "member" }, { "email": "dervan@caltech.edu", "id": "Dervan-P-B", "name": { "family": "Dervan", "given": "Peter B." }, "role": "member" }, { "id": "Collins-T-J", "name": { "family": "Collins", "given": "Terrence J." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1981-08-27", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1982", "author_list": "Najdzionek, Jan Stanley", "advisor_list": "Collins, Terrence J.", "comittee_list": "Anson, Fred C.; Gray, Harry B.; et el." } ]