doi:10.1021/acs.organomet.5c00356engVillanueva Alli, IñigoOñate, EnriqueOliván, MontserratPolyhydride Osmium-Mediated Hydrosilylation of Carbonyl Compounds: Intermediates and MechanismART-2025-146481OsH6(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.2025http://zaguan.unizar.es/record/16502810.1021/acs.organomet.5c00356http://zaguan.unizar.es/record/165028oai:zaguan.unizar.es:165028info:eu-repo/grantAgreement/ES/AEI/PID2023-146967NB-I00info:eu-repo/grantAgreement/ES/DGA/E06-23ROrganometallics 44 (2025), 2749-2762All rights reservedhttp://www.europeana.eu/rights/rr-f/info:eu-repo/semantics/embargoedAccess