Cross-dehydrogenative coupling of secondary amines with silanes catalyzed by agostic iridium-NSi species

An active catalytic system for the cross-dehydrogenative coupling (CDC) of a wide range of secondary amines with silanes is reported. The iridium(III) derivatives [Ir(H)(X)(κ2-NSiDMQ)(L)] (NSiDMQ = {4,8-dimethylquinoline-2-yloxy}dimethylsilyl; L = coe, X = Cl, 2; L = coe, X = OTf, 3; L = PCy3, X = C...

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Autores: Padilla, Marina, Batuecas, María, García-Orduña, Pilar, Fernández, Israel, Fernández-Álvarez, Francisco J.
Tipo de recurso: artículo
Estado:Versión publicada
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:10261/391518
Acceso en línea:http://hdl.handle.net/10261/391518
Access Level:acceso abierto
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spelling Cross-dehydrogenative coupling of secondary amines with silanes catalyzed by agostic iridium-NSi speciesPadilla, MarinaBatuecas, MaríaGarcía-Orduña, PilarFernández, IsraelFernández-Álvarez, Francisco J.An active catalytic system for the cross-dehydrogenative coupling (CDC) of a wide range of secondary amines with silanes is reported. The iridium(III) derivatives [Ir(H)(X)(κ2-NSiDMQ)(L)] (NSiDMQ = {4,8-dimethylquinoline-2-yloxy}dimethylsilyl; L = coe, X = Cl, 2; L = coe, X = OTf, 3; L = PCy3, X = Cl, 4; L = PCy3, X = OTf, 5), which are stabilized by a weak yet noticeable Ir···H-C agostic interaction between the iridium and one of the C-H bonds of the 8-Me substituent of the NSiDMQ ligand, have been prepared and fully characterized. These species have proven to be effective catalysts for the CDC of secondary amines with hydrosilanes. The best catalytic performance (TOF1/2 = 79,300 h-1) was obtained using 5 (0.25 mol %), N-methylaniline, and HSiMe2Ph. The catalytic activity of the species [Ir(H)(OTf)(κ2-NSiQ)(PCy3)] (10, NSiQ = {quinoline-2-yloxy}dimethylsilyl) and [Ir(H)(OTf)(κ2-NSiMQ)(PCy3)] (11, NSiMQ = {4-methylquinoline-2-yloxy}dimethylsilyl), related to 5 but lacking the 8-Me substituent, is markedly lower than that found for 5. This fact highlights the crucial role of the 8-Me substituent of the NSiDMQ ligand in enhancing the catalytic performance of these iridium complexes.Financial support from grants PID2021-126212OB-I00, PID2022-139318NB-I00, and RED2022-134331-T, funded by MICIU/AEI/10.13039/501100011033 and DGA/FSE project E42_23R (Gobierno de Aragón), is gratefully acknowledged. F.J.F.-A. and M.B. thank Campus Iberus and European Union’s Horizon 2020 research and innovation program under the Marie Skłodowska program─Grant Agreement No. 101034288.Peer reviewedAmerican Chemical SocietyAgencia Estatal de Investigación (España)Ministerio de Ciencia, Innovación y Universidades (España)European CommissionGobierno de AragónCampus Iberus - Campus de Excelencia Internacional del Valle del EbroConsejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202520252025info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://hdl.handle.net/10261/391518reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2021-126212OB-I00info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2022-139318NB-I00info:eu-repo/grantAgreement/AEI//RED2022-134331-Tinfo:eu-repo/grantAgreement/EC/H2020/101034288Padilla, Marina; Batuecas, María; García-Orduña, Pilar; Fernández, Israel; Fernández-Álvarez, Francisco J.; 2025; Supporting Information: Cross-dehydrogenative coupling of secondary amines with silanes catalyzed by agostic iridium-NSi species [Dataset]; American Chemical Society; https://doi.org/10.1021/acs.inorgchem.4c04512https://doi.org/10.1021/acs.inorgchem.4c04512Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/3915182026-05-22T06:33:51Z
dc.title.none.fl_str_mv Cross-dehydrogenative coupling of secondary amines with silanes catalyzed by agostic iridium-NSi species
title Cross-dehydrogenative coupling of secondary amines with silanes catalyzed by agostic iridium-NSi species
spellingShingle Cross-dehydrogenative coupling of secondary amines with silanes catalyzed by agostic iridium-NSi species
Padilla, Marina
title_short Cross-dehydrogenative coupling of secondary amines with silanes catalyzed by agostic iridium-NSi species
title_full Cross-dehydrogenative coupling of secondary amines with silanes catalyzed by agostic iridium-NSi species
title_fullStr Cross-dehydrogenative coupling of secondary amines with silanes catalyzed by agostic iridium-NSi species
title_full_unstemmed Cross-dehydrogenative coupling of secondary amines with silanes catalyzed by agostic iridium-NSi species
title_sort Cross-dehydrogenative coupling of secondary amines with silanes catalyzed by agostic iridium-NSi species
dc.creator.none.fl_str_mv Padilla, Marina
Batuecas, María
García-Orduña, Pilar
Fernández, Israel
Fernández-Álvarez, Francisco J.
author Padilla, Marina
author_facet Padilla, Marina
Batuecas, María
García-Orduña, Pilar
Fernández, Israel
Fernández-Álvarez, Francisco J.
author_role author
author2 Batuecas, María
García-Orduña, Pilar
Fernández, Israel
Fernández-Álvarez, Francisco J.
author2_role author
author
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
Campus Iberus - Campus de Excelencia Internacional del Valle del Ebro
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
description An active catalytic system for the cross-dehydrogenative coupling (CDC) of a wide range of secondary amines with silanes is reported. The iridium(III) derivatives [Ir(H)(X)(κ2-NSiDMQ)(L)] (NSiDMQ = {4,8-dimethylquinoline-2-yloxy}dimethylsilyl; L = coe, X = Cl, 2; L = coe, X = OTf, 3; L = PCy3, X = Cl, 4; L = PCy3, X = OTf, 5), which are stabilized by a weak yet noticeable Ir···H-C agostic interaction between the iridium and one of the C-H bonds of the 8-Me substituent of the NSiDMQ ligand, have been prepared and fully characterized. These species have proven to be effective catalysts for the CDC of secondary amines with hydrosilanes. The best catalytic performance (TOF1/2 = 79,300 h-1) was obtained using 5 (0.25 mol %), N-methylaniline, and HSiMe2Ph. The catalytic activity of the species [Ir(H)(OTf)(κ2-NSiQ)(PCy3)] (10, NSiQ = {quinoline-2-yloxy}dimethylsilyl) and [Ir(H)(OTf)(κ2-NSiMQ)(PCy3)] (11, NSiMQ = {4-methylquinoline-2-yloxy}dimethylsilyl), related to 5 but lacking the 8-Me substituent, is markedly lower than that found for 5. This fact highlights the crucial role of the 8-Me substituent of the NSiDMQ ligand in enhancing the catalytic performance of these iridium complexes.
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
Publisher's version
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/391518
url http://hdl.handle.net/10261/391518
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv #PLACEHOLDER_PARENT_METADATA_VALUE#
#PLACEHOLDER_PARENT_METADATA_VALUE#
#PLACEHOLDER_PARENT_METADATA_VALUE#
#PLACEHOLDER_PARENT_METADATA_VALUE#
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2021-126212OB-I00
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2022-139318NB-I00
info:eu-repo/grantAgreement/AEI//RED2022-134331-T
info:eu-repo/grantAgreement/EC/H2020/101034288
Padilla, Marina; Batuecas, María; García-Orduña, Pilar; Fernández, Israel; Fernández-Álvarez, Francisco J.; 2025; Supporting Information: Cross-dehydrogenative coupling of secondary amines with silanes catalyzed by agostic iridium-NSi species [Dataset]; American Chemical Society; https://doi.org/10.1021/acs.inorgchem.4c04512
https://doi.org/10.1021/acs.inorgchem.4c04512
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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