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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Authors: Villanueva Alli, Iñigo, Oñate, Enrique, Oliván, Montserrat
Format: article
Status:Published version
Publication Date:2026
Country:España
Institution:Universidad de Zaragoza
Repository:Zaguán. Repositorio Digital de la Universidad de Zaragoza
OAI Identifier:oai:dnet:zaguan______::2cfd8b9cd4805682fbad5e2591fd2e13
Online Access:http://zaguan.unizar.es/record/171282
Access Level:Open access
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spelling Si–O Bond Formation Mediated by an Osmium-Polyhydride: Dehydrogenative Silylation of Alcohols and Tandem Hydrosilylation/Dehydrogenative Silylation of SalicylaldehydesVillanueva Alli, IñigoOñate, 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. SN - 0020-16692026info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://zaguan.unizar.es/record/171282reponame:Zaguán. Repositorio Digital de la Universidad de Zaragozainstname:Universidad de ZaragozaInglésinfo:eu-repo/grantAgreement/ES/AEI/PID2023-146967NB-I00info:eu-repo/grantAgreement/ES/DGA/E06-23Rinfo:eu-repo/semantics/openAccessoai:dnet:zaguan______::2cfd8b9cd4805682fbad5e2591fd2e132026-05-29T13:59:51Z
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
Villanueva Alli, Iñigo
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 Villanueva Alli, Iñigo
Oñate, Enrique
Oliván, Montserrat
author Villanueva Alli, Iñigo
author_facet Villanueva Alli, Iñigo
Oñate, Enrique
Oliván, Montserrat
author_role author
author2 Oñate, Enrique
Oliván, Montserrat
author2_role author
author
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. SN - 0020-1669
publishDate 2026
dc.date.none.fl_str_mv 2026
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://zaguan.unizar.es/record/171282
url http://zaguan.unizar.es/record/171282
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/grantAgreement/ES/AEI/PID2023-146967NB-I00
info:eu-repo/grantAgreement/ES/DGA/E06-23R
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
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dc.source.none.fl_str_mv reponame:Zaguán. Repositorio Digital de la Universidad de Zaragoza
instname:Universidad de Zaragoza
instname_str Universidad de Zaragoza
reponame_str Zaguán. Repositorio Digital de la Universidad de Zaragoza
collection Zaguán. Repositorio Digital de la Universidad de Zaragoza
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