Hybrid Catalysts Comprised of Graphene Modified with Rhodium-Based N-Heterocyclic Carbenes for Alkyne Hydrosilylation

Thermally partially reduced graphene oxide has been covalently modified with 3-methyl-4-phenyl-1, 2, 3-triazolium salts making use of the epoxy functionalities on the carbon nanomaterial. Characterization of the functionalized materials through adequate solid characterization techniques, particularl...

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Autores: Sanchez-Page, B., Jimenez, M.V., Perez-Torrente, J.J., Passarelli, V., Blasco, J., Subias, G., Granda, M., Alvarez, P.
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2020
País:España
Institución:Universidad de Zaragoza
Repositorio:Zaguán. Repositorio Digital de la Universidad de Zaragoza
OAI Identifier:oai:zaguan.unizar.es:127881
Acceso en línea:http://zaguan.unizar.es/record/127881
Access Level:acceso abierto
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spelling Hybrid Catalysts Comprised of Graphene Modified with Rhodium-Based N-Heterocyclic Carbenes for Alkyne HydrosilylationSanchez-Page, B.Jimenez, M.V.Perez-Torrente, J.J.Passarelli, V.Blasco, J.Subias, G.Granda, M.Alvarez, P.Thermally partially reduced graphene oxide has been covalently modified with 3-methyl-4-phenyl-1, 2, 3-triazolium salts making use of the epoxy functionalities on the carbon nanomaterial. Characterization of the functionalized materials through adequate solid characterization techniques, particularly X-ray photoelectron spectroscopy (XPS), allows one to follow the stepwise building up of the triazolium fragments on the graphene oxide attached to the wall via covalent C-N linkage. The hydroxyl-triazolium-functionalized materials have been used to prepare rhodium hybrid materials containing either alkoxo or triazolylidene molecular rhodium(I) complexes depending on the protection of the hydroxyl groups present in the material. Characterization of the heterogeneous systems, especially by means of XPS and extended X-ray absorption fine structure (EXAFS) spectroscopy, has evidenced the coordination sphere of the supported rhodium(I) complexes in both rhodium hybrid materials. The graphene-oxide-supported rhodium triazolylidene hybrid catalysts show excellent activity, comparable to that of the homogeneous [RhI(cod)(Triaz)] (Triaz = 1, 4-diphenyl-3-methyl-1, 2, 3-triazol-5-ylidene) catalyst, for the hydrosilylation of terminal and internal alkynes. In addition, these catalysts have shown good selectivity to the beta-(Z) vinylsilane isomers (for the not hindered terminal substrates) or syn-additions (for the internal substrates). In contrast to the rhodium(I)-alkoxo-based hybrid material, the silyl-protected rhodium(I)-triazolylidene-based hybrid catalyst can be reused in consecutive cycles without loss of activity maintaining the selectivity. The lack of leaching of active rhodium species demonstrates the strength of the C-N covalent bond of the triazolylidene linker to the graphitic wall.2020info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersionapplication/pdfhttp://zaguan.unizar.es/record/127881reponame:Zaguán. Repositorio Digital de la Universidad de Zaragozainstname:Universidad de ZaragozaInglésinfo:eu-repo/grantAgreement/ES/DGA/E12-R17info:eu-repo/grantAgreement/ES/DGA-FSE/Building Europe from Aragoninfo:eu-repo/grantAgreement/ES/DGA-FSE/E42-17Rinfo:eu-repo/grantAgreement/ES/MICINN-FEDER/CTQ2016-75884-Pinfo:eu-repo/grantAgreement/ES/MICINN-FEDER/RTI2018-098537-B-C22info:eu-repo/semantics/openAccessoai:zaguan.unizar.es:1278812026-05-29T13:59:51Z
dc.title.none.fl_str_mv Hybrid Catalysts Comprised of Graphene Modified with Rhodium-Based N-Heterocyclic Carbenes for Alkyne Hydrosilylation
title Hybrid Catalysts Comprised of Graphene Modified with Rhodium-Based N-Heterocyclic Carbenes for Alkyne Hydrosilylation
spellingShingle Hybrid Catalysts Comprised of Graphene Modified with Rhodium-Based N-Heterocyclic Carbenes for Alkyne Hydrosilylation
Sanchez-Page, B.
title_short Hybrid Catalysts Comprised of Graphene Modified with Rhodium-Based N-Heterocyclic Carbenes for Alkyne Hydrosilylation
title_full Hybrid Catalysts Comprised of Graphene Modified with Rhodium-Based N-Heterocyclic Carbenes for Alkyne Hydrosilylation
title_fullStr Hybrid Catalysts Comprised of Graphene Modified with Rhodium-Based N-Heterocyclic Carbenes for Alkyne Hydrosilylation
title_full_unstemmed Hybrid Catalysts Comprised of Graphene Modified with Rhodium-Based N-Heterocyclic Carbenes for Alkyne Hydrosilylation
title_sort Hybrid Catalysts Comprised of Graphene Modified with Rhodium-Based N-Heterocyclic Carbenes for Alkyne Hydrosilylation
dc.creator.none.fl_str_mv Sanchez-Page, B.
Jimenez, M.V.
Perez-Torrente, J.J.
Passarelli, V.
Blasco, J.
Subias, G.
Granda, M.
Alvarez, P.
author Sanchez-Page, B.
author_facet Sanchez-Page, B.
Jimenez, M.V.
Perez-Torrente, J.J.
Passarelli, V.
Blasco, J.
Subias, G.
Granda, M.
Alvarez, P.
author_role author
author2 Jimenez, M.V.
Perez-Torrente, J.J.
Passarelli, V.
Blasco, J.
Subias, G.
Granda, M.
Alvarez, P.
author2_role author
author
author
author
author
author
author
description Thermally partially reduced graphene oxide has been covalently modified with 3-methyl-4-phenyl-1, 2, 3-triazolium salts making use of the epoxy functionalities on the carbon nanomaterial. Characterization of the functionalized materials through adequate solid characterization techniques, particularly X-ray photoelectron spectroscopy (XPS), allows one to follow the stepwise building up of the triazolium fragments on the graphene oxide attached to the wall via covalent C-N linkage. The hydroxyl-triazolium-functionalized materials have been used to prepare rhodium hybrid materials containing either alkoxo or triazolylidene molecular rhodium(I) complexes depending on the protection of the hydroxyl groups present in the material. Characterization of the heterogeneous systems, especially by means of XPS and extended X-ray absorption fine structure (EXAFS) spectroscopy, has evidenced the coordination sphere of the supported rhodium(I) complexes in both rhodium hybrid materials. The graphene-oxide-supported rhodium triazolylidene hybrid catalysts show excellent activity, comparable to that of the homogeneous [RhI(cod)(Triaz)] (Triaz = 1, 4-diphenyl-3-methyl-1, 2, 3-triazol-5-ylidene) catalyst, for the hydrosilylation of terminal and internal alkynes. In addition, these catalysts have shown good selectivity to the beta-(Z) vinylsilane isomers (for the not hindered terminal substrates) or syn-additions (for the internal substrates). In contrast to the rhodium(I)-alkoxo-based hybrid material, the silyl-protected rhodium(I)-triazolylidene-based hybrid catalyst can be reused in consecutive cycles without loss of activity maintaining the selectivity. The lack of leaching of active rhodium species demonstrates the strength of the C-N covalent bond of the triazolylidene linker to the graphitic wall.
publishDate 2020
dc.date.none.fl_str_mv 2020
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv http://zaguan.unizar.es/record/127881
url http://zaguan.unizar.es/record/127881
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/grantAgreement/ES/DGA/E12-R17
info:eu-repo/grantAgreement/ES/DGA-FSE/Building Europe from Aragon
info:eu-repo/grantAgreement/ES/DGA-FSE/E42-17R
info:eu-repo/grantAgreement/ES/MICINN-FEDER/CTQ2016-75884-P
info:eu-repo/grantAgreement/ES/MICINN-FEDER/RTI2018-098537-B-C22
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
publisher.none.fl_str_mv
dc.source.none.fl_str_mv reponame:Zaguán. Repositorio Digital de la Universidad de Zaragoza
instname:Universidad de Zaragoza
instname_str Universidad de Zaragoza
reponame_str Zaguán. Repositorio Digital de la Universidad de Zaragoza
collection Zaguán. Repositorio Digital de la Universidad de Zaragoza
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