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Shapley, Patricia A. Allen, Jana Leanne 2011-05-07T12:41:04Z 2011-05-07T12:41:04Z 10000-01-01 1996 Osmium-chromium heterobimetallic complexes of the type (Y) (M(N)$\rm R\sb2(\mu$-O)$\rm\sb2CrO\sb2$) (Y = NBu$\sb4$, PPh$\sb4$; M = Os, Ru; R = Me, CH$\rm\sb2SiMe\sb3$, C$\rm\sb6H\sb5$) act as catalysts for the oxidation of primary and secondary alcohols to the corresponding aldehydes and ketones using dioxygen as the secondary oxidant. These complexes also catalyze the oxidation of 1,2-bis(diphenylphosphino)ethane (dppe) to the corresponding phosphine oxide, Ph$\sb2$P(O)CH$\rm\sb2CH\sb2P(O)Ph\sb2$. None of the singly oxidized phosphine is detected. Investigations into the kinetics of the oxidation reactions showed the oxidation of benzyl alcohol to benzaldehyde is first order in both alcohol and catalyst concentration. A mechanism involving coordination of the alcohol to the osmium center, followed by proton transfer and $\beta$-hydrogen elimination of the products yields a reduced osmium-chromium complex. This reduced complex can react with dioxygen to form a bridging peroxo complex that can react with a molecule of the reduced complex to regenerate two equivalents of the original heterobimetallic complex. Dioxygen labeling studies in the oxidation of dppe are described. Based on these experiments, two potential mechanisms are proposed for the oxidation of dppe. Routes toward the synthesis of a chiral version of the heterobimetallic catalyst utilizing a chiral counterion or an alkyl group derived from S-2-methylbutane, 2,2$\sp\prime$-dimethylbinaphthyl, camphene, 9,10-dibromocamphor and 2-norbornane are described. The synthesis of several new inorganic and organometallic compounds of osmium are described: (PPh$\rm\sb4\rbrack\lbrack Os(N)(CH\sb2SiMe\sb3)\sb2(\mu$-O)$\rm\sb2CrO\sb2\rbrack,$ trans- (PPh$\rm\sb4\rbrack\lbrack Os(N)(CH\sb2SiMe \sb3)\sb2Br\sb2$), (N(n-Bu)$\rm\sb4\rbrack\lbrack Os(N)(C\sb6H\sb5)\sb4$), (N(n-Bu)$\rm\sb4\rbrack\lbrack Os(N)(C\sb6H\sb5)\sb2Cl\sb2\rbrack,\ Os(N)(C\sb6H\sb5)\sb3$(py), (N(n-Bu)$\rm\sb4\rbrack\lbrack Os(N)(C\sb6H\sb5)\sb2(\mu$-O)$\rm\sb2CrO\sb2$), (PPh$\rm\sb4\rbrack\lbrack Os(N)(CH\sb2SiMe\sb3)\sb2(dppe)(O$-CrO$ \sb3$)), (N(n-Bu)$\rm\sb4\rbrack\lbrack Os(N)(CH\sb2SiMe\sb3)\sb2(dppe)(O$-CrO$\rm\sb3$)), (N(n-Bu)$\rm\sb4\rbrack\lbrack Os(N)(CH\sb2SiMe\sb3)\sb2(dppe)(O$-SO$\rm\sb3$)), ((R)-PhCH(Me)NMe$\rm\sb3\rbrack\lbrack Os(N)Cl\sb4$), ((R)-PhCH(Me)NMe$\rm\sb3\rbrack\lbrack Os(N)(OSiMe\sb3)\sb4$), ((R)-PhCH(Me)NMe$\rm\sb3\rbrack\lbrack Os(N)(CH\sb3)\sb4\rbrack,\ \lbrack PPh\sb4\rbrack\lbrack Os(N)(CH\sb2SiMe\sb3)\sb3Br\rbrack.$ Made available in DSpace on 2011-05-07T12:41:04Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9712188.pdf: 8313921 bytes, checksum: b135313eb67b78623c5be99daf32956c (MD5) Previous issue date: 1996 Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:44:19Z Item is restricted indefinitely. Restriction data tranferred 2014-07-01T11:19:30-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission ETDs are only available to UIUC Users without author permission U of I Only 9780591197297 AAI9712188 (UMI)AAI9712188 http://hdl.handle.net/2142/20502 eng Copyright 1996 Allen, Jana Leanne Chemistry, Inorganic Chemistry, Organic Synthesis and reactivity of osmium-chromium oxidation catalysts and routes to a chiral analog text Chemistry Chemistry University of Illinois at Urbana-Champaign Dissertation Ph.D.