Ligand Effects in Carbon−Boron Coupling Processes Mediated by σ-BH Platinum Complexes

The reaction of tri-coordinated boranes (derived from dioxaborolanes and diazaborolanes) with cyclometalated low-electron count platinum complexes [Pt(NHC’)(NHC)][BArF] (NHC=ItBuiPr, IMes, IMes*) led, at low temperature, to the formation of the corresponding σ-BH species. Some of these species have...

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Detalhes bibliográficos
Autores: Ríos Moreno, Pablo, Fernández de Córdova, Francisco José, Borge, Javier, Curado, Natalia, Lledós, Agustí, Conejero, Salvador
Tipo de documento: artigo
Estado:Versão publicada
Data de publicação:2021
País:España
Recursos:Universidad de Sevilla (US)
Repositório:idUS. Depósito de Investigación de la Universidad de Sevilla
OAI Identifier:oai:idus.us.es:11441/135009
Acesso em linha:https://hdl.handle.net/11441/135009
https://doi.org/10.1002/ejic.202100428
Access Level:Acceso aberto
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spelling Ligand Effects in Carbon−Boron Coupling Processes Mediated by σ-BH Platinum ComplexesRíos Moreno, PabloFernández de Córdova, Francisco JoséBorge, JavierCurado, NataliaLledós, AgustíConejero, SalvadorThe reaction of tri-coordinated boranes (derived from dioxaborolanes and diazaborolanes) with cyclometalated low-electron count platinum complexes [Pt(NHC’)(NHC)][BArF] (NHC=ItBuiPr, IMes, IMes*) led, at low temperature, to the formation of the corresponding σ-BH species. Some of these species have been characterized by X-Ray diffraction methods showing a rare η1-coordination mode. These compounds are thermally unstable and undergo a carbon-boron coupling process whose reversibility depends on the NHC ligand. DFT calculations indicate that the energy barriers required for C−B bond formation events (together with Pt−H bonds) are lower than the competitive reactions leading to C−H bond formation (and Pt−B bonds). However, the C−B coupling products appear to be formed under kinetic control with ItBuiPr ligands, whereas the relative low energy barrier leading to C−H bond formation is sufficiently low to form the thermodynamically more stable platinum boryl complexes at rt. The latter energy barrier is, nevertheless, too high for the systems bearing IMes and IMes* ligands.Ministerio de Ciencia e Innovación y Fondos FEDER PID-2020-116861GB-I00, PID2019-109312GB-I00 and RED2018-102387-TCSIC AEPP_CTQ2016-76267-PWileyQuímica InorgánicaMinisterio de Ciencia e Innovación (MICIN). EspañaConsejo Superior de Investigaciones Científicas (CSIC)European Commission (EC). Fondo Europeo de Desarrollo Regional (FEDER)2021info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionapplication/pdfapplication/pdfhttps://hdl.handle.net/11441/135009https://doi.org/10.1002/ejic.202100428reponame:idUS. Depósito de Investigación de la Universidad de Sevillainstname:Universidad de Sevilla (US)InglésEuropean Journal of Inorganic Chemistry, 2021 (35), 3528-3539.PID-2020-116861GB-I00PID2019-109312GB-I00RED2018-102387-Thttps://dx.doi.org/10.1002/ejic.202100428info:eu-repo/semantics/openAccessoai:idus.us.es:11441/1350092026-06-17T12:51:07Z
dc.title.none.fl_str_mv Ligand Effects in Carbon−Boron Coupling Processes Mediated by σ-BH Platinum Complexes
title Ligand Effects in Carbon−Boron Coupling Processes Mediated by σ-BH Platinum Complexes
spellingShingle Ligand Effects in Carbon−Boron Coupling Processes Mediated by σ-BH Platinum Complexes
Ríos Moreno, Pablo
title_short Ligand Effects in Carbon−Boron Coupling Processes Mediated by σ-BH Platinum Complexes
title_full Ligand Effects in Carbon−Boron Coupling Processes Mediated by σ-BH Platinum Complexes
title_fullStr Ligand Effects in Carbon−Boron Coupling Processes Mediated by σ-BH Platinum Complexes
title_full_unstemmed Ligand Effects in Carbon−Boron Coupling Processes Mediated by σ-BH Platinum Complexes
title_sort Ligand Effects in Carbon−Boron Coupling Processes Mediated by σ-BH Platinum Complexes
dc.creator.none.fl_str_mv Ríos Moreno, Pablo
Fernández de Córdova, Francisco José
Borge, Javier
Curado, Natalia
Lledós, Agustí
Conejero, Salvador
author Ríos Moreno, Pablo
author_facet Ríos Moreno, Pablo
Fernández de Córdova, Francisco José
Borge, Javier
Curado, Natalia
Lledós, Agustí
Conejero, Salvador
author_role author
author2 Fernández de Córdova, Francisco José
Borge, Javier
Curado, Natalia
Lledós, Agustí
Conejero, Salvador
author2_role author
author
author
author
author
dc.contributor.none.fl_str_mv Química Inorgánica
Ministerio de Ciencia e Innovación (MICIN). España
Consejo Superior de Investigaciones Científicas (CSIC)
European Commission (EC). Fondo Europeo de Desarrollo Regional (FEDER)
description The reaction of tri-coordinated boranes (derived from dioxaborolanes and diazaborolanes) with cyclometalated low-electron count platinum complexes [Pt(NHC’)(NHC)][BArF] (NHC=ItBuiPr, IMes, IMes*) led, at low temperature, to the formation of the corresponding σ-BH species. Some of these species have been characterized by X-Ray diffraction methods showing a rare η1-coordination mode. These compounds are thermally unstable and undergo a carbon-boron coupling process whose reversibility depends on the NHC ligand. DFT calculations indicate that the energy barriers required for C−B bond formation events (together with Pt−H bonds) are lower than the competitive reactions leading to C−H bond formation (and Pt−B bonds). However, the C−B coupling products appear to be formed under kinetic control with ItBuiPr ligands, whereas the relative low energy barrier leading to C−H bond formation is sufficiently low to form the thermodynamically more stable platinum boryl complexes at rt. The latter energy barrier is, nevertheless, too high for the systems bearing IMes and IMes* ligands.
publishDate 2021
dc.date.none.fl_str_mv 2021
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 https://hdl.handle.net/11441/135009
https://doi.org/10.1002/ejic.202100428
url https://hdl.handle.net/11441/135009
https://doi.org/10.1002/ejic.202100428
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv European Journal of Inorganic Chemistry, 2021 (35), 3528-3539.
PID-2020-116861GB-I00
PID2019-109312GB-I00
RED2018-102387-T
https://dx.doi.org/10.1002/ejic.202100428
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Wiley
publisher.none.fl_str_mv Wiley
dc.source.none.fl_str_mv reponame:idUS. Depósito de Investigación de la Universidad de Sevilla
instname:Universidad de Sevilla (US)
instname_str Universidad de Sevilla (US)
reponame_str idUS. Depósito de Investigación de la Universidad de Sevilla
collection idUS. Depósito de Investigación de la Universidad de Sevilla
repository.name.fl_str_mv
repository.mail.fl_str_mv
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