Nickel-Catalyzed Deuteration of Primary, Secondary, and Tertiary Silanes: Scope and Mechanistic Insights

Chemicals and CAS Registry Numbers nickel 7440-02-0 silane 7803-62-5

Detalles Bibliográficos
Autores: Laglera-Gándara, Carlos J., Jiménez-Rioboó, Rafael, Álvarez-Rodríguez, Lucía, Peloso, Riccardo, Río González, Pablo del, Rodríguez, Amor
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:10261/393406
Acceso en línea:http://hdl.handle.net/10261/393406
https://api.elsevier.com/content/abstract/scopus_id/105003017575
Access Level:acceso abierto
Palabra clave:Catalysts
Energy
Group 14 compounds
Hydrogen isotopes
Inorganic compounds
http://metadata.un.org/sdg/3
Ensure healthy lives and promote well-being for all at all ages
catalysts
inorganic compounds
hydrogen isotopes
energy
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spelling Nickel-Catalyzed Deuteration of Primary, Secondary, and Tertiary Silanes: Scope and Mechanistic InsightsLaglera-Gándara, Carlos J.Jiménez-Rioboó, RafaelÁlvarez-Rodríguez, LucíaPeloso, RiccardoRío González, Pablo delRodríguez, AmorCatalystsEnergyGroup 14 compoundsHydrogen isotopesInorganic compoundshttp://metadata.un.org/sdg/3Ensure healthy lives and promote well-being for all at all agescatalystsinorganic compoundshydrogen isotopesenergyChemicals and CAS Registry Numbers nickel 7440-02-0 silane 7803-62-5Deuterated silanes are crucial reagents for deuteration, with a diverse range of applications in materials science, pharmaceuticals, and isotopic labeling. While most methods for synthesizing deuterated silanes rely on stoichiometric environmentally harmful processes or noble metal catalysts, research into more sustainable alternatives has received relatively less attention. In this study, we introduce a catalyst based on a nickel PBP-pincer system (PBP = bis(phosphino)boryl), which effectively facilitates catalytic hydrogen/deuterium exchange for primary, secondary, and tertiary silanes, as well as tertiary siloxanes and certain boranes, utilizing a catalyst loading of 2 mol % at 25 °C. DFT calculations identify two reaction pathways that require overcoming similar energy barriers for the H/D exchange step: silane activation assisted by the PBP ligand (ΔG⧧ = 24.1 kcal mol-1) and H/D exchange promoted by nucleophilic Ni-hydride (ΔG⧧ = 22.4 kcal mol-1). These results suggest that both pathways are feasible, with a slight energetic preference for the latter. We also present detailed mechanistic studies, including control experiments, an analysis of catalyst deactivation pathways, and kinetic studies that are in excellent agreement with the outcome of the theoretical calculations.This work was supported by the Spanish MCIN/AEI/10.13039/501100011033 (Grants PID2019-109312GB-I00, PID2022-141925NB-I00, and RED2022-134287-T), European FEDER funds, and the Junta de Andalucía (project P20_00513). C.J.L.-G. thanks for a Margarita Salas grant financed by the European Union-Next Generation EU, Ministry of Universities and Recovery, Transformation and Resilience Plan, through a call from the University of Oviedo (Grant MU-21-UP2021-030 53307942). The use of the computational facilities of the Supercomputing Center of Galicia (CESGA) is gratefully acknowledged.Peer reviewedAmerican Chemical SocietyMinisterio de Ciencia e Innovación (España)Junta de AndalucíaEuropean CommissionUniversidad de OviedoCentro de Supercomputación de GaliciaLaglera-Gándara, Carlos J. [0000-0002-4480-1315]Jiménez-Rioboó, Rafael [0000-0002-9545-0172]Álvarez-Rodríguez, Lucía [0000-0003-3176-3855]Peloso, Riccardo [0000-0002-9532-7609]Río González, Pablo del [l0000-0003-4467-4157]Rodríguez, Amor [0000-0001-9194-5613]Consejo 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/10261/393406https://api.elsevier.com/content/abstract/scopus_id/105003017575reponame: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#info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-109312GB-I00info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2022-141925NB-I00info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/RED2022-134287-Thttps://doi.org/10.1021/acs.joc.5c00107Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/3934062026-05-22T06:33:51Z
dc.title.none.fl_str_mv Nickel-Catalyzed Deuteration of Primary, Secondary, and Tertiary Silanes: Scope and Mechanistic Insights
title Nickel-Catalyzed Deuteration of Primary, Secondary, and Tertiary Silanes: Scope and Mechanistic Insights
spellingShingle Nickel-Catalyzed Deuteration of Primary, Secondary, and Tertiary Silanes: Scope and Mechanistic Insights
Laglera-Gándara, Carlos J.
Catalysts
Energy
Group 14 compounds
Hydrogen isotopes
Inorganic compounds
http://metadata.un.org/sdg/3
Ensure healthy lives and promote well-being for all at all ages
catalysts
inorganic compounds
hydrogen isotopes
energy
title_short Nickel-Catalyzed Deuteration of Primary, Secondary, and Tertiary Silanes: Scope and Mechanistic Insights
title_full Nickel-Catalyzed Deuteration of Primary, Secondary, and Tertiary Silanes: Scope and Mechanistic Insights
title_fullStr Nickel-Catalyzed Deuteration of Primary, Secondary, and Tertiary Silanes: Scope and Mechanistic Insights
title_full_unstemmed Nickel-Catalyzed Deuteration of Primary, Secondary, and Tertiary Silanes: Scope and Mechanistic Insights
title_sort Nickel-Catalyzed Deuteration of Primary, Secondary, and Tertiary Silanes: Scope and Mechanistic Insights
dc.creator.none.fl_str_mv Laglera-Gándara, Carlos J.
Jiménez-Rioboó, Rafael
Álvarez-Rodríguez, Lucía
Peloso, Riccardo
Río González, Pablo del
Rodríguez, Amor
author Laglera-Gándara, Carlos J.
author_facet Laglera-Gándara, Carlos J.
Jiménez-Rioboó, Rafael
Álvarez-Rodríguez, Lucía
Peloso, Riccardo
Río González, Pablo del
Rodríguez, Amor
author_role author
author2 Jiménez-Rioboó, Rafael
Álvarez-Rodríguez, Lucía
Peloso, Riccardo
Río González, Pablo del
Rodríguez, Amor
author2_role author
author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Ciencia e Innovación (España)
Junta de Andalucía
European Commission
Universidad de Oviedo
Centro de Supercomputación de Galicia
Laglera-Gándara, Carlos J. [0000-0002-4480-1315]
Jiménez-Rioboó, Rafael [0000-0002-9545-0172]
Álvarez-Rodríguez, Lucía [0000-0003-3176-3855]
Peloso, Riccardo [0000-0002-9532-7609]
Río González, Pablo del [l0000-0003-4467-4157]
Rodríguez, Amor [0000-0001-9194-5613]
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv Catalysts
Energy
Group 14 compounds
Hydrogen isotopes
Inorganic compounds
http://metadata.un.org/sdg/3
Ensure healthy lives and promote well-being for all at all ages
catalysts
inorganic compounds
hydrogen isotopes
energy
topic Catalysts
Energy
Group 14 compounds
Hydrogen isotopes
Inorganic compounds
http://metadata.un.org/sdg/3
Ensure healthy lives and promote well-being for all at all ages
catalysts
inorganic compounds
hydrogen isotopes
energy
description Chemicals and CAS Registry Numbers nickel 7440-02-0 silane 7803-62-5
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/10261/393406
https://api.elsevier.com/content/abstract/scopus_id/105003017575
url http://hdl.handle.net/10261/393406
https://api.elsevier.com/content/abstract/scopus_id/105003017575
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#
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-109312GB-I00
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2022-141925NB-I00
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/RED2022-134287-T
https://doi.org/10.1021/acs.joc.5c00107
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
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