Air-Stable 14-Electron Rhodium(III) Complexes Bearing Si,N Ligands as Catalysts in Hydrolysis of Silanes

Unsaturated 14-electron Rh(III) complexes are of great interest because of their involvement in stoichiometric and catalytic processes. Herein, we report the synthesis and characterization of one neutral and three cationic Rh(III) complexes bearing Si,N ligands, two of which are putative 14-electron...

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Autores: Prieto Pascual, Unai, Alli, Iñigo V., Bustos Rosas, Itxaso, Vitorica Yrezabal, Iñigo J., Matxain Beraza, Jon Mattin, Freixa Fernández, Zoraida, Huertos Mansilla, Miguel Angel
Tipo de recurso: artículo
Fecha de publicación:2023
País:España
Institución:Universidad del País Vasco
Repositorio:Addi. Archivo Digital para la Docencia y la Investigación
OAI Identifier:oai:addi.ehu.eus:10810/65174
Acceso en línea:http://hdl.handle.net/10810/65174
Access Level:acceso abierto
Palabra clave:catalysts
hydrolysis
ligands
metals
Silicon
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spelling Air-Stable 14-Electron Rhodium(III) Complexes Bearing Si,N Ligands as Catalysts in Hydrolysis of SilanesPrieto Pascual, UnaiAlli, Iñigo V.Bustos Rosas, ItxasoVitorica Yrezabal, Iñigo J.Matxain Beraza, Jon MattinFreixa Fernández, ZoraidaHuertos Mansilla, Miguel AngelcatalystshydrolysisligandsmetalsSiliconUnsaturated 14-electron Rh(III) complexes are of great interest because of their involvement in stoichiometric and catalytic processes. Herein, we report the synthesis and characterization of one neutral and three cationic Rh(III) complexes bearing Si,N ligands, two of which are putative 14-electron cationic complexes. The reaction of the rhodium(I) precursor [RhCl(coe)2]2 with 8-(dimethylsilyl)quinoline (L1) resulted in the formation of the neutral rhodium(III) complex {Rh(Cl)(κ2-L1)2} (1-L1). From this compound, the cationic complex {Rh(κ2-L1)2(NCMe)}[BAr4F] (2-L1) can be synthesized by abstraction of the chlorine with Na[BAr4F]. The neutral complexes based on 8-(dimethylsilyl)-2-methylquinoline (L2) and 4-(dimethylsilyl)-9-phenylacridine (L3) could not be synthesized due to the bulky nature of the ligands. Therefore, the cationic compounds {Rh(κ2-L2)2}[BAr4F] (2-L2) and {Rh(κ2-L3)2}[BAr4F] (2-L3) were synthesized directly and proved to be very stable (solid and solution). Experimental (NMR and X-ray) and theoretical (NBO, QTAIM, and NCI) studies were performed and determined that the stability of the complexes is provided by weak agostic interactions. Furthermore, the cationic complexes were found to be active as catalysts in the hydrolysis of dihydrosilanes.This publication is part of the projects PID2019-111281GB-I00 funded by MCIN/AEI/10.13039/501100011033 and IT1741-22 and IT1553-22 founded by Gobierno Vasco. The authors thank SGiker for technical and human support. Universidad del Pais Vasco (to U.P. PIF18/026) and IKERBASQUE (to M.H and Z.F.) are acknowledge for personel funding. I. B. thank to Spanish Ministry of Universities and European Union (Margarita Salas grant funded by the Next-GenerationEU, MARSA21/16). I. V-Y thanks Junta de Andalucía (P21_00386) for funding202420242023info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10810/65174reponame:Addi. Archivo Digital para la Docencia y la Investigacióninstname:Universidad del País VascoInglésinfo:eu-repo/grantAgreement/MICIN/PID2019-111281GB-I00/https://pubs.acs.org/doi/10.1021/acs.organomet.3c00324info:eu-repo/semantics/openAccess© 2023 American Chemical Societyoai:addi.ehu.eus:10810/651742026-06-18T09:23:17Z
dc.title.none.fl_str_mv Air-Stable 14-Electron Rhodium(III) Complexes Bearing Si,N Ligands as Catalysts in Hydrolysis of Silanes
title Air-Stable 14-Electron Rhodium(III) Complexes Bearing Si,N Ligands as Catalysts in Hydrolysis of Silanes
spellingShingle Air-Stable 14-Electron Rhodium(III) Complexes Bearing Si,N Ligands as Catalysts in Hydrolysis of Silanes
Prieto Pascual, Unai
catalysts
hydrolysis
ligands
metals
Silicon
title_short Air-Stable 14-Electron Rhodium(III) Complexes Bearing Si,N Ligands as Catalysts in Hydrolysis of Silanes
title_full Air-Stable 14-Electron Rhodium(III) Complexes Bearing Si,N Ligands as Catalysts in Hydrolysis of Silanes
title_fullStr Air-Stable 14-Electron Rhodium(III) Complexes Bearing Si,N Ligands as Catalysts in Hydrolysis of Silanes
title_full_unstemmed Air-Stable 14-Electron Rhodium(III) Complexes Bearing Si,N Ligands as Catalysts in Hydrolysis of Silanes
title_sort Air-Stable 14-Electron Rhodium(III) Complexes Bearing Si,N Ligands as Catalysts in Hydrolysis of Silanes
dc.creator.none.fl_str_mv Prieto Pascual, Unai
Alli, Iñigo V.
Bustos Rosas, Itxaso
Vitorica Yrezabal, Iñigo J.
Matxain Beraza, Jon Mattin
Freixa Fernández, Zoraida
Huertos Mansilla, Miguel Angel
author Prieto Pascual, Unai
author_facet Prieto Pascual, Unai
Alli, Iñigo V.
Bustos Rosas, Itxaso
Vitorica Yrezabal, Iñigo J.
Matxain Beraza, Jon Mattin
Freixa Fernández, Zoraida
Huertos Mansilla, Miguel Angel
author_role author
author2 Alli, Iñigo V.
Bustos Rosas, Itxaso
Vitorica Yrezabal, Iñigo J.
Matxain Beraza, Jon Mattin
Freixa Fernández, Zoraida
Huertos Mansilla, Miguel Angel
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv catalysts
hydrolysis
ligands
metals
Silicon
topic catalysts
hydrolysis
ligands
metals
Silicon
description Unsaturated 14-electron Rh(III) complexes are of great interest because of their involvement in stoichiometric and catalytic processes. Herein, we report the synthesis and characterization of one neutral and three cationic Rh(III) complexes bearing Si,N ligands, two of which are putative 14-electron cationic complexes. The reaction of the rhodium(I) precursor [RhCl(coe)2]2 with 8-(dimethylsilyl)quinoline (L1) resulted in the formation of the neutral rhodium(III) complex {Rh(Cl)(κ2-L1)2} (1-L1). From this compound, the cationic complex {Rh(κ2-L1)2(NCMe)}[BAr4F] (2-L1) can be synthesized by abstraction of the chlorine with Na[BAr4F]. The neutral complexes based on 8-(dimethylsilyl)-2-methylquinoline (L2) and 4-(dimethylsilyl)-9-phenylacridine (L3) could not be synthesized due to the bulky nature of the ligands. Therefore, the cationic compounds {Rh(κ2-L2)2}[BAr4F] (2-L2) and {Rh(κ2-L3)2}[BAr4F] (2-L3) were synthesized directly and proved to be very stable (solid and solution). Experimental (NMR and X-ray) and theoretical (NBO, QTAIM, and NCI) studies were performed and determined that the stability of the complexes is provided by weak agostic interactions. Furthermore, the cationic complexes were found to be active as catalysts in the hydrolysis of dihydrosilanes.
publishDate 2023
dc.date.none.fl_str_mv 2023
2024
2024
dc.type.none.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/10810/65174
url http://hdl.handle.net/10810/65174
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/grantAgreement/MICIN/PID2019-111281GB-I00/
https://pubs.acs.org/doi/10.1021/acs.organomet.3c00324
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
© 2023 American Chemical Society
eu_rights_str_mv openAccess
rights_invalid_str_mv © 2023 American Chemical Society
dc.format.none.fl_str_mv application/pdf
dc.source.none.fl_str_mv reponame:Addi. Archivo Digital para la Docencia y la Investigación
instname:Universidad del País Vasco
instname_str Universidad del País Vasco
reponame_str Addi. Archivo Digital para la Docencia y la Investigación
collection Addi. Archivo Digital para la Docencia y la Investigación
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15.300719

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