Si−O Bond Formation Mediated by an Osmium-Polyhydride: Dehydrogenative Silylation of Alcohols and Tandem Hydrosilylation/Dehydrogenative Silylation of Salicylaldehydes

OsH5(SiHPh2)(PiPr3)2 (1) catalyzes the monoalcoholysis of diphenylsilane with a variety of alcohols. Density functional theory (DFT) calculations suggest that the reactions occur via a highly ordered transition state resulting from the nucleophilic attack of the alcohol to the silane coordinated to...

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Autores: Alli, Iñigo V., Oñate, Enrique, Oliván, Montserrat
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2026
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:dnet:digitalcsic_::bd2de37505e1e6cfbfab37365b83f62f
Acceso en línea:http://hdl.handle.net/10261/432238
Access Level:acceso abierto
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spelling Si−O Bond Formation Mediated by an Osmium-Polyhydride: Dehydrogenative Silylation of Alcohols and Tandem Hydrosilylation/Dehydrogenative Silylation of SalicylaldehydesAlli, Iñigo V.Oñate, EnriqueOliván, MontserratOsH5(SiHPh2)(PiPr3)2 (1) catalyzes the monoalcoholysis of diphenylsilane with a variety of alcohols. Density functional theory (DFT) calculations suggest that the reactions occur via a highly ordered transition state resulting from the nucleophilic attack of the alcohol to the silane coordinated to the osmium center in an η1-H–SiHPh2 fashion. The alcoholysis or aminolysis of the Si–H bond of 1 with 2-hydroxypyridine or 2-aminopyridine affords OsH3{κ2-Si,N-(SiPh2-E-py)}(PiPr3)2 (E = O (4), NH (5)). Analogously, OsH4(SiH2Ph)2(PiPr3)2 (2) reacts with 2-hydroxypyridine and 2-aminopyridine to give OsH3{κ2-Si,N-(SiPh(Epy)-E-py)}(PiPr3)2 (E = O (6), NH (7)), as a result of the alcoholysis or aminolysis, respectively, of both Si–H bonds of one of the phenylsilyl ligands. Additionally, 1 catalyzes the tandem hydrosilylation/dehydrogenative silylation of salicylaldehydes with diphenylsilane to afford silacycles. DFT calculations suggest that this process happens via an outer-sphere hydrogenation of the aldehyde moiety to give a diol and tetrahydride-silylene OsH4(=SiPh2)(PiPr3)2. Next, the silylative dehydrogenation of the Ph–OH function affords a silyl-O-functionalized pentahydride, which, upon the nucleophilic intramolecular attack of the benzylic OH group, gives the silacycle and intermediate OsH4(η2-H2)(PiPr3)2, which reacts with diphenylsilane, giving H2 and regenerating OsH5(SiHPh2)(PiPr3)2.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 the allocation of computational resources. Authors would like to acknowledge the use of Servicio General de Apoyo a la Investigación-SAI, Universidad de Zaragoza.Peer reviewedAmerican Chemical SocietyAgencia Estatal de Investigación (España)Ministerio de Ciencia, Innovación y Universidades (España)European Commission202620262026info:eu-repo/semantics/articlePublisher's versioninfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://hdl.handle.net/10261/432238reponame: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; 2026; Supporting Information: Si−O Bond Formation Mediated by an Osmium-Polyhydride: Dehydrogenative Silylation of Alcohols and Tandem Hydrosilylation/Dehydrogenative Silylation of Salicylaldehydes [Dataset]; American Chemical Society; https://doi.org/10.1021/acs.inorgchem.6c01007https://doi.org/10.1021/acs.inorgchem.6c01007Síinfo:eu-repo/semantics/openAccessoai:dnet:digitalcsic_::bd2de37505e1e6cfbfab37365b83f62f2026-05-22T06:33:51Z
dc.title.none.fl_str_mv Si−O Bond Formation Mediated by an Osmium-Polyhydride: Dehydrogenative Silylation of Alcohols and Tandem Hydrosilylation/Dehydrogenative Silylation of Salicylaldehydes
title Si−O Bond Formation Mediated by an Osmium-Polyhydride: Dehydrogenative Silylation of Alcohols and Tandem Hydrosilylation/Dehydrogenative Silylation of Salicylaldehydes
spellingShingle Si−O Bond Formation Mediated by an Osmium-Polyhydride: Dehydrogenative Silylation of Alcohols and Tandem Hydrosilylation/Dehydrogenative Silylation of Salicylaldehydes
Alli, Iñigo V.
title_short Si−O Bond Formation Mediated by an Osmium-Polyhydride: Dehydrogenative Silylation of Alcohols and Tandem Hydrosilylation/Dehydrogenative Silylation of Salicylaldehydes
title_full Si−O Bond Formation Mediated by an Osmium-Polyhydride: Dehydrogenative Silylation of Alcohols and Tandem Hydrosilylation/Dehydrogenative Silylation of Salicylaldehydes
title_fullStr Si−O Bond Formation Mediated by an Osmium-Polyhydride: Dehydrogenative Silylation of Alcohols and Tandem Hydrosilylation/Dehydrogenative Silylation of Salicylaldehydes
title_full_unstemmed Si−O Bond Formation Mediated by an Osmium-Polyhydride: Dehydrogenative Silylation of Alcohols and Tandem Hydrosilylation/Dehydrogenative Silylation of Salicylaldehydes
title_sort Si−O Bond Formation Mediated by an Osmium-Polyhydride: Dehydrogenative Silylation of Alcohols and Tandem Hydrosilylation/Dehydrogenative Silylation of Salicylaldehydes
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
description OsH5(SiHPh2)(PiPr3)2 (1) catalyzes the monoalcoholysis of diphenylsilane with a variety of alcohols. Density functional theory (DFT) calculations suggest that the reactions occur via a highly ordered transition state resulting from the nucleophilic attack of the alcohol to the silane coordinated to the osmium center in an η1-H–SiHPh2 fashion. The alcoholysis or aminolysis of the Si–H bond of 1 with 2-hydroxypyridine or 2-aminopyridine affords OsH3{κ2-Si,N-(SiPh2-E-py)}(PiPr3)2 (E = O (4), NH (5)). Analogously, OsH4(SiH2Ph)2(PiPr3)2 (2) reacts with 2-hydroxypyridine and 2-aminopyridine to give OsH3{κ2-Si,N-(SiPh(Epy)-E-py)}(PiPr3)2 (E = O (6), NH (7)), as a result of the alcoholysis or aminolysis, respectively, of both Si–H bonds of one of the phenylsilyl ligands. Additionally, 1 catalyzes the tandem hydrosilylation/dehydrogenative silylation of salicylaldehydes with diphenylsilane to afford silacycles. DFT calculations suggest that this process happens via an outer-sphere hydrogenation of the aldehyde moiety to give a diol and tetrahydride-silylene OsH4(=SiPh2)(PiPr3)2. Next, the silylative dehydrogenation of the Ph–OH function affords a silyl-O-functionalized pentahydride, which, upon the nucleophilic intramolecular attack of the benzylic OH group, gives the silacycle and intermediate OsH4(η2-H2)(PiPr3)2, which reacts with diphenylsilane, giving H2 and regenerating OsH5(SiHPh2)(PiPr3)2.
publishDate 2026
dc.date.none.fl_str_mv 2026
2026
2026
dc.type.none.fl_str_mv info:eu-repo/semantics/article
Publisher's version
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/432238
url http://hdl.handle.net/10261/432238
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; 2026; Supporting Information: Si−O Bond Formation Mediated by an Osmium-Polyhydride: Dehydrogenative Silylation of Alcohols and Tandem Hydrosilylation/Dehydrogenative Silylation of Salicylaldehydes [Dataset]; American Chemical Society; https://doi.org/10.1021/acs.inorgchem.6c01007
https://doi.org/10.1021/acs.inorgchem.6c01007
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
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
collection DIGITAL.CSIC. Repositorio Institucional del CSIC
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