σ-Silane Platinum(II) Complexes as Intermediates in C−Si Bond-Coupling Processes

Platinum complexes [Pt(NHC′)(NHC)][BAr] (in which NHC′ denotes a cyclometalated N-heterocyclic carbene ligand, NHC) react with primary silanes RSiH to afford the cyclometalated platinum(II) silyl complexes [Pt(NHC-SiHR′)(NHC)][BAr] through a process that involves the formation of C−Si and Pt−Si bond...

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Autores: Ríos, Pablo, Fouilloux, Hugo, Díez, Josefina, Vidossich, Pietro, Lledós, Agustí, Conejero, Salvador
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2019
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/199970
Acceso en línea:http://hdl.handle.net/10261/199970
Access Level:acceso abierto
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spelling σ-Silane Platinum(II) Complexes as Intermediates in C−Si Bond-Coupling ProcessesRíos, PabloFouilloux, HugoDíez, JosefinaVidossich, PietroLledós, AgustíConejero, SalvadorPlatinum complexes [Pt(NHC′)(NHC)][BAr] (in which NHC′ denotes a cyclometalated N-heterocyclic carbene ligand, NHC) react with primary silanes RSiH to afford the cyclometalated platinum(II) silyl complexes [Pt(NHC-SiHR′)(NHC)][BAr] through a process that involves the formation of C−Si and Pt−Si bonds with concomitant extrusion of H. Low-temperature NMR studies indicate that the process proceeds through initial formation of the σ-SiH complexes [Pt(NHC′)(NHC)(HSiHR)][BAr], which are stable at temperatures below −10 °C. At higher temperatures, activation of one Si−H bond followed by a C−Si coupling reaction generates an agostic SiH platinum hydride derivative [Pt(H)(NHC′-SiHR)(NHC)][BAr], which undergoes a second Si−H bond activation to afford the final products. Computational modeling of the reaction mechanism indicates that the stereochemistry of the silyl/hydride ligands after the first Si−H bond cleavage dictates the nature of the products, favoring the formation of a C−Si bond over a C−H bond, in contrast to previous results obtained for tertiary silanes. Furthermore, the process involves a trans-to-cis isomerization of the NHC ligand before the second Si−H bond cleavage.John Wiley & SonsConsejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]2020202020192020info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Postprintinfo:eu-repo/semantics/acceptedVersionhttp://hdl.handle.net/10261/199970reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Ingléshttp://dx.doi.org/10.1002/chem.201902226Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/1999702026-05-22T06:33:51Z
dc.title.none.fl_str_mv σ-Silane Platinum(II) Complexes as Intermediates in C−Si Bond-Coupling Processes
title σ-Silane Platinum(II) Complexes as Intermediates in C−Si Bond-Coupling Processes
spellingShingle σ-Silane Platinum(II) Complexes as Intermediates in C−Si Bond-Coupling Processes
Ríos, Pablo
title_short σ-Silane Platinum(II) Complexes as Intermediates in C−Si Bond-Coupling Processes
title_full σ-Silane Platinum(II) Complexes as Intermediates in C−Si Bond-Coupling Processes
title_fullStr σ-Silane Platinum(II) Complexes as Intermediates in C−Si Bond-Coupling Processes
title_full_unstemmed σ-Silane Platinum(II) Complexes as Intermediates in C−Si Bond-Coupling Processes
title_sort σ-Silane Platinum(II) Complexes as Intermediates in C−Si Bond-Coupling Processes
dc.creator.none.fl_str_mv Ríos, Pablo
Fouilloux, Hugo
Díez, Josefina
Vidossich, Pietro
Lledós, Agustí
Conejero, Salvador
author Ríos, Pablo
author_facet Ríos, Pablo
Fouilloux, Hugo
Díez, Josefina
Vidossich, Pietro
Lledós, Agustí
Conejero, Salvador
author_role author
author2 Fouilloux, Hugo
Díez, Josefina
Vidossich, Pietro
Lledós, Agustí
Conejero, Salvador
author2_role author
author
author
author
author
dc.contributor.none.fl_str_mv Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
description Platinum complexes [Pt(NHC′)(NHC)][BAr] (in which NHC′ denotes a cyclometalated N-heterocyclic carbene ligand, NHC) react with primary silanes RSiH to afford the cyclometalated platinum(II) silyl complexes [Pt(NHC-SiHR′)(NHC)][BAr] through a process that involves the formation of C−Si and Pt−Si bonds with concomitant extrusion of H. Low-temperature NMR studies indicate that the process proceeds through initial formation of the σ-SiH complexes [Pt(NHC′)(NHC)(HSiHR)][BAr], which are stable at temperatures below −10 °C. At higher temperatures, activation of one Si−H bond followed by a C−Si coupling reaction generates an agostic SiH platinum hydride derivative [Pt(H)(NHC′-SiHR)(NHC)][BAr], which undergoes a second Si−H bond activation to afford the final products. Computational modeling of the reaction mechanism indicates that the stereochemistry of the silyl/hydride ligands after the first Si−H bond cleavage dictates the nature of the products, favoring the formation of a C−Si bond over a C−H bond, in contrast to previous results obtained for tertiary silanes. Furthermore, the process involves a trans-to-cis isomerization of the NHC ligand before the second Si−H bond cleavage.
publishDate 2019
dc.date.none.fl_str_mv 2019
2020
2020
2020
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/10261/199970
url http://hdl.handle.net/10261/199970
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv http://dx.doi.org/10.1002/chem.201902226
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv John Wiley & Sons
publisher.none.fl_str_mv John Wiley & Sons
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
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,812429

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