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Girolami, Gregory S. Jefferis, Jesse M. 2015-09-25T22:14:45Z 2015-09-25T22:14:45Z 10000-01-01 2000 2000 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). No. of bitstreams: 2 license.txt: 4848 bytes, checksum: 96035ab3f5e1c23cc7138a224ce498bd (MD5) 9990027.pdf: 4516888 bytes, checksum: 6768f7f530a2cc56bd81c62a236fe297 (MD5) Previous issue date: 2000 Embargo set by: Seth Robbins for item 85764 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs U of I Only 116 p. Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 2000. http://hdl.handle.net/2142/84483 (MiAaPQ)AAI9990027 eng Chemistry, Inorganic New Chemistry of Transition Metal Alkyls and Hydrides: Bonding and Reactivity text Chemistry Chemistry University of Illinois at Urbana-Champaign Dissertation Ph.D.