000165028 001__ 165028
000165028 005__ 20251204150239.0
000165028 0247_ $$2doi$$a10.1021/acs.organomet.5c00356
000165028 0248_ $$2sideral$$a146481
000165028 037__ $$aART-2025-146481
000165028 041__ $$aeng
000165028 100__ $$aVillanueva Alli, Iñigo$$uUniversidad de Zaragoza
000165028 245__ $$aPolyhydride Osmium-Mediated Hydrosilylation of Carbonyl Compounds: Intermediates and Mechanism
000165028 260__ $$c2025
000165028 5060_ $$aAccess copy available to the general public$$fUnrestricted
000165028 5203_ $$aOsH6(PiPr3)2 (1) reacts with phenylsilane to afford OsH5(SiH2Ph)(PiPr3)2 (2), which reacts with additional phenylsilane to give OsH4(SiH2Ph)2(PiPr3)2 (3). The reaction of 1 with diphenylsilane affords OsH5(SiHPh2)(PiPr3)2 (4), which in the presence of diphenylsilane and traces of water leads to OsH4{κ2-Si,Si-(Ph2Si–O–SiPh2)}(PiPr3)2 (5). Complex 4 promotes the hydrosilylation of aldehydes with H2SiPh2 to give silyl ethers, while for ketones mixtures of hydrosilylation and dehydrogenative silylation products are obtained. The reactions of 4 with benzaldehyde and acetone afford OsH5{Si(OR)Ph2}(PiPr3)2 (R = CH2Ph (6), iPr (7)), which undergo a metathesis between a Si–Ph bond and a C(sp3)–H bond of one methyl group of one phosphine to give OsH4{κ1-P,η2-SiH-[iPr2PCH(Me)CH2Si(OR)PhH]}(PiPr3) (R = CH2Ph (8), iPr (9)). The combination of experimental findings and density functional theory calculations has permitted to establish the mechanism for the hydrosilylation processes. The key intermediate is the tetrahydride-silylene OsH4(=SiPh2)(PiPr3)2, formed by an outer-sphere hydrogenation of the carbonyl group promoted by a trihydride(dihydrogen) isomer of 4. For enolyzable ketones, this pathway competes with one where the enol form directly attacks the Si atom of 4, affording silyl enol ethers and a tetrahydride(dihydrogen) isomer of 1, that reacts with diphenylsilane to release hydrogen and close the cycle.
000165028 536__ $$9info:eu-repo/grantAgreement/ES/AEI/PID2023-146967NB-I00$$9info:eu-repo/grantAgreement/ES/DGA/E06-23R
000165028 540__ $$9info:eu-repo/semantics/embargoedAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000165028 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000165028 700__ $$0(orcid)0000-0003-2094-719X$$aOñate, Enrique
000165028 700__ $$0(orcid)0000-0003-0381-0917$$aOliván, Montserrat
000165028 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000165028 773__ $$g(2025), [14 pp.]$$pOrganometallics$$tOrganometallics$$x0276-7333
000165028 8564_ $$s1447313$$uhttps://zaguan.unizar.es/record/165028/files/texto_completo.pdf$$yPostprint$$zinfo:eu-repo/date/embargoEnd/2026-11-18
000165028 8564_ $$s1120481$$uhttps://zaguan.unizar.es/record/165028/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint$$zinfo:eu-repo/date/embargoEnd/2026-11-18
000165028 909CO $$ooai:zaguan.unizar.es:165028$$particulos$$pdriver
000165028 951__ $$a2025-12-04-14:39:36
000165028 980__ $$aARTICLE