{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/84483"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/84483","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"New Chemistry of Transition Metal Alkyls and Hydrides: Bonding and Reactivity","abstract":"Protonation of the osmium(II) hydrides (C5Me5)Os(PR 3)2H with tetrafluoroboric acid affords the corresponding osmium(IV) dihydride complexes of stoichiometry [(C5Me5)Os(PR 3)2H2+], where PR3 = PMe3, PEt3, PPh3, 1/2 dmpe, 1/2 dmpm, 1/2 dppm, or 1/2 dpdtm (where dmpe = 1,2-bis(dimethylphosphino)ethane, dmpm = bis(dimethylphosphino)methane, dppm = bis(diphenylphosphino)methane, and dpdtm = (diphenylphosphino)(di-p-tolylphosphino)methane. In the cisoid compounds [(C5Me5)Os(dmpm)H2 +] and [(C5Me5)Os(dppm)H2 +], the two hydride ligands undergo chemical exchange on the NMR time scale with activation free energies of 17.5 and 16.9 kcal mol-1 , respectively. Protonation of all the (C5Me5)Os(PR 3)2H complexes at low temperature affords the cisoid isomers, which must be the kinetic products. For the compounds [(C5Me 5)Os(PMe3)2H2+] and [(C5Me5)Os(PPh3)2H2 +], the cisoid isomers convert to the transoid isomers by two pathways, one unimolecular and one bimolecular; the latter involves intermolecular hydride exchange between the dihydride cations and the neutral monohydride.","abstract_html":"Protonation of the osmium(II) hydrides (C5Me5)Os(PR 3)2H with tetrafluoroboric acid affords the corresponding osmium(IV) dihydride complexes of stoichiometry [(C5Me5)Os(PR 3)2H2+], where PR3 = PMe3, PEt3, PPh3, 1/2 dmpe, 1/2 dmpm, 1/2 dppm, or 1/2 dpdtm (where dmpe = 1,2-bis(dimethylphosphino)ethane, dmpm = bis(dimethylphosphino)methane, dppm = bis(diphenylphosphino)methane, and dpdtm = (diphenylphosphino)(di-p-tolylphosphino)methane. In the cisoid compounds [(C5Me5)Os(dmpm)H2 +] and [(C5Me5)Os(dppm)H2 +], the two hydride ligands undergo chemical exchange on the NMR time scale with activation free energies of 17.5 and 16.9 kcal mol-1 , respectively. Protonation of all the (C5Me5)Os(PR 3)2H complexes at low temperature affords the cisoid isomers, which must be the kinetic products. For the compounds [(C5Me 5)Os(PMe3)2H2+] and [(C5Me5)Os(PPh3)2H2 +], the cisoid isomers convert to the transoid isomers by two pathways, one unimolecular and one bimolecular; the latter involves intermolecular hydride exchange between the dihydride cations and the neutral monohydride.","abstract_has_math":false,"creators":["Jefferis, Jesse M."],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Girolami, Gregory S."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2015,"date_issued":"2015-09-25T22:14:45Z","date_published":"2015-09-25T22:14:45Z","updated_at":"2026-07-22T22:26:23Z","subjects":["Chemistry, Inorganic"],"languages":["eng"],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(MiAaPQ)AAI9990027"],"render_values":[{"text":"(MiAaPQ)AAI9990027","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/84483","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Girolami, Gregory S."]},{"key":"dc:creator","label":"Author","values":["Jefferis, Jesse M."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2015-09-25T22:14:45Z","10000-01-01","2000"]},{"key":"dc:type","label":"Dc Type","values":["text"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Dissertation"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Ph.D."]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["University of Illinois at Urbana-Champaign"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemistry, Inorganic"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/84483","(MiAaPQ)AAI9990027"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Protonation of the osmium(II) hydrides (C5Me5)Os(PR 3)2H with tetrafluoroboric acid affords the corresponding osmium(IV) dihydride complexes of stoichiometry [(C5Me5)Os(PR 3)2H2+], where PR3 = PMe3, PEt3, PPh3, 1/2 dmpe, 1/2 dmpm, 1/2 dppm, or 1/2 dpdtm (where dmpe = 1,2-bis(dimethylphosphino)ethane, dmpm = bis(dimethylphosphino)methane, dppm = bis(diphenylphosphino)methane, and dpdtm = (diphenylphosphino)(di-p-tolylphosphino)methane. In the cisoid compounds [(C5Me5)Os(dmpm)H2 +] and [(C5Me5)Os(dppm)H2 +], the two hydride ligands undergo chemical exchange on the NMR time scale with activation free energies of 17.5 and 16.9 kcal mol-1 , respectively. Protonation of all the (C5Me5)Os(PR 3)2H complexes at low temperature affords the cisoid isomers, which must be the kinetic products. For the compounds [(C5Me 5)Os(PMe3)2H2+] and [(C5Me5)Os(PPh3)2H2 +], the cisoid isomers convert to the transoid isomers by two pathways, one unimolecular and one bimolecular; the latter involves intermolecular hydride exchange between the dihydride cations and the neutral monohydride.","Made available in DSpace on 2015-09-25T22:14:45Z (GMT). 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In the cisoid compounds [(C5Me5)Os(dmpm)H2 +] and [(C5Me5)Os(dppm)H2 +], the two hydride ligands undergo chemical exchange on the NMR time scale with activation free energies of 17.5 and 16.9 kcal mol-1 , respectively. Protonation of all the (C5Me5)Os(PR 3)2H complexes at low temperature affords the cisoid isomers, which must be the kinetic products. For the compounds [(C5Me 5)Os(PMe3)2H2+] and [(C5Me5)Os(PPh3)2H2 +], the cisoid isomers convert to the transoid isomers by two pathways, one unimolecular and one bimolecular; the latter involves intermolecular hydride exchange between the dihydride cations and the neutral monohydride.","Made available in DSpace on 2015-09-25T22:14:45Z (GMT). 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