Polyhydride osmium-mediated hydrosilylation of carbonyl compounds: Intermediates and mechanism

OsH6(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...

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Autores: Alli, Iñigo V., Oñate, Enrique, Oliván, Montserrat
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2025
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/409456
Acceso en línea:http://hdl.handle.net/10261/409456
Access Level:acceso embargado
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spelling Polyhydride osmium-mediated hydrosilylation of carbonyl compounds: Intermediates and mechanismAlli, Iñigo V.Oñate, EnriqueOliván, MontserratOsH6(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.Financial support from the MICIU/AEI/10.13039/501100011033 (PID2023-146967NB-I00), Gobierno de Aragón (E06_23R), FEDER, and the European Social Fund is acknowledged. BIFI (Instituto de Biocomputación y Física de Sistemas Complejos) and CESGA (Centro de Supercomputación de Galicia) are acknowledged for allocation of computational resources.Peer reviewedAmerican Chemical SocietyAgencia Estatal de Investigación (España)Ministerio de Ciencia, Innovación y Universidades (España)European CommissionGobierno de AragónConsejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202520252025info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Postprintinfo:eu-repo/semantics/acceptedVersionapplication/pdfhttp://hdl.handle.net/10261/409456reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2023-146967NB-I00Alli, Iñigo V.; Oñate, Enrique; Oliván, Montserrat; 2025; Supporting Information: Polyhydride osmium-mediated hydrosilylation of carbonyl compounds: Intermediates and mechanism [Dataset]; American Chemical Society; https://doi.org/10.1021/acs.organomet.5c00356https://doi.org/10.1021/acs.organomet.5c00356Síinfo:eu-repo/semantics/embargoedAccessoai:digital.csic.es:10261/4094562026-05-22T06:33:51Z
dc.title.none.fl_str_mv Polyhydride osmium-mediated hydrosilylation of carbonyl compounds: Intermediates and mechanism
title Polyhydride osmium-mediated hydrosilylation of carbonyl compounds: Intermediates and mechanism
spellingShingle Polyhydride osmium-mediated hydrosilylation of carbonyl compounds: Intermediates and mechanism
Alli, Iñigo V.
title_short Polyhydride osmium-mediated hydrosilylation of carbonyl compounds: Intermediates and mechanism
title_full Polyhydride osmium-mediated hydrosilylation of carbonyl compounds: Intermediates and mechanism
title_fullStr Polyhydride osmium-mediated hydrosilylation of carbonyl compounds: Intermediates and mechanism
title_full_unstemmed Polyhydride osmium-mediated hydrosilylation of carbonyl compounds: Intermediates and mechanism
title_sort Polyhydride osmium-mediated hydrosilylation of carbonyl compounds: Intermediates and mechanism
dc.creator.none.fl_str_mv Alli, Iñigo V.
Oñate, Enrique
Oliván, Montserrat
author Alli, Iñigo V.
author_facet Alli, Iñigo V.
Oñate, Enrique
Oliván, Montserrat
author_role author
author2 Oñate, Enrique
Oliván, Montserrat
author2_role author
author
dc.contributor.none.fl_str_mv Agencia Estatal de Investigación (España)
Ministerio de Ciencia, Innovación y Universidades (España)
European Commission
Gobierno de Aragón
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
description OsH6(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.
publishDate 2025
dc.date.none.fl_str_mv 2025
2025
2025
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Postprint
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/409456
url http://hdl.handle.net/10261/409456
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv #PLACEHOLDER_PARENT_METADATA_VALUE#
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2023-146967NB-I00
Alli, Iñigo V.; Oñate, Enrique; Oliván, Montserrat; 2025; Supporting Information: Polyhydride osmium-mediated hydrosilylation of carbonyl compounds: Intermediates and mechanism [Dataset]; American Chemical Society; https://doi.org/10.1021/acs.organomet.5c00356
https://doi.org/10.1021/acs.organomet.5c00356
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/embargoedAccess
eu_rights_str_mv embargoedAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
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