Recyclable Homogeneous Catalysis Enabled by Dynamic Coordination on Rhodium(II) Axial Sites of Metal-Organic Polyhedra

The activity of catalytic nanoparticles is strongly dependent on their surface chemistry, which controls colloidal stability and substrate diffusion toward catalytic sites. In this work, we studied how the outer surface chemistry of nanostructured Rh(II)-based metal-organic cages or polyhedra (Rh-MO...

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Autores: Sánchez-Fuente, Miguel, Hernández-López, Laura, Maspoch, Daniel, Mas-Ballesté, Rubén, Carné-Sánchez, Arnau
Formato: artículo
Estado:Versión publicada
Fecha de publicación:2024
País:España
Recursos:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/381094
Acesso em linha:http://hdl.handle.net/10261/381094
https://api.elsevier.com/content/abstract/scopus_id/85198356157
Access Level:acceso abierto
Palavra-chave:Homogenous catalysis
Ligand exchange
Metal-organic polyhedral
Rh(II) catalysis
Supramolecular surface chemistry
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spelling Recyclable Homogeneous Catalysis Enabled by Dynamic Coordination on Rhodium(II) Axial Sites of Metal-Organic PolyhedraSánchez-Fuente, MiguelHernández-López, LauraMaspoch, DanielMas-Ballesté, RubénCarné-Sánchez, ArnauHomogenous catalysisLigand exchangeMetal-organic polyhedralRh(II) catalysisSupramolecular surface chemistryThe activity of catalytic nanoparticles is strongly dependent on their surface chemistry, which controls colloidal stability and substrate diffusion toward catalytic sites. In this work, we studied how the outer surface chemistry of nanostructured Rh(II)-based metal-organic cages or polyhedra (Rh-MOPs) impacts their performance in homogeneous catalysis. Specifically, through post-synthetic coordination of aliphatic imidazole ligands onto the exohedral Rh(II) axial sites of Rh-MOPs, we solubilized a cuboctahedral Rh-MOP in dichloromethane, thereby enabling its use as a homogeneous catalyst. We demonstrated that the presence of the coordinating ligand on the surface of the Rh-MOP does not hinder its catalytic activity in styrene aziridination and cyclopropanation reactions, thanks to the dynamic Rh-imidazole coordination bond. Finally, we used similar ligand exchange post-synthetic reactions to develop a ligand-mediated approach for precipitating the Rh-MOP catalyst, facilitating the recovery and reuse of Rh-MOPs as homogeneous catalysts.M. S.-F. and L. H.-L. contributed equally to this work. This work was supported by the Spanish MINECO (project RTI2018-095622-B−I00, PID2019-110637RB−I00 and PID2022-141016OB−I00) and the Catalan AGAUR (project 2021 SGR 00458). It was also funded by the CERCA Programme/Generalitat de Catalunya and through a fellowship (LCF/BQ/PR20/11770011) from the “la Caixa” Foundation (ID 100010434). ICN2 is supported by the Severo Ochoa Centres of Excellence programme, Grant CEX2021-001214-S, funded by MCIN/AEI/10.13039.501100011033. A.C.S. is indebted to the Ramón y Cajal Program (RYC2020-029749-I Fellowship) and the Europa Excelencia grant (EUR2021-121997) L.H.L acknowledges the support from the Spanish State Research Agency (PRE2019-088056). M.S.-F. thanks Ministerio de Ciencia e Innovación for a FPI contract (PRE2020-092295).With funding from the Spanish government through the "Severo Ochoa Centre of Excelence" accreditation (CEX2021-001214-S)Peer reviewedWiley-VCHMinisterio de Economía y Competitividad (España)Agencia Estatal de Investigación (España)Generalitat de CatalunyaFundación la CaixaMinisterio de Ciencia e Innovación (España)European CommissionMaspoch, Daniel [0000-0003-1325-9161]Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202520252024info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://hdl.handle.net/10261/381094https://api.elsevier.com/content/abstract/scopus_id/85198356157reponame: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##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/RTI2018-095622-B−I00info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-110637RB−I00info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2022-141016OB−I00info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/CEX2021-001214-Sinfo:eu-repo/grantAgreement/AEI//RYC2020-029749-IThe underlying dataset has been published as supplementary material of the article in the publisher platform at DOI 10.1002/chem.202401661https://doi.org/10.1002/chem.202401661Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/3810942026-05-22T06:33:51Z
dc.title.none.fl_str_mv Recyclable Homogeneous Catalysis Enabled by Dynamic Coordination on Rhodium(II) Axial Sites of Metal-Organic Polyhedra
title Recyclable Homogeneous Catalysis Enabled by Dynamic Coordination on Rhodium(II) Axial Sites of Metal-Organic Polyhedra
spellingShingle Recyclable Homogeneous Catalysis Enabled by Dynamic Coordination on Rhodium(II) Axial Sites of Metal-Organic Polyhedra
Sánchez-Fuente, Miguel
Homogenous catalysis
Ligand exchange
Metal-organic polyhedral
Rh(II) catalysis
Supramolecular surface chemistry
title_short Recyclable Homogeneous Catalysis Enabled by Dynamic Coordination on Rhodium(II) Axial Sites of Metal-Organic Polyhedra
title_full Recyclable Homogeneous Catalysis Enabled by Dynamic Coordination on Rhodium(II) Axial Sites of Metal-Organic Polyhedra
title_fullStr Recyclable Homogeneous Catalysis Enabled by Dynamic Coordination on Rhodium(II) Axial Sites of Metal-Organic Polyhedra
title_full_unstemmed Recyclable Homogeneous Catalysis Enabled by Dynamic Coordination on Rhodium(II) Axial Sites of Metal-Organic Polyhedra
title_sort Recyclable Homogeneous Catalysis Enabled by Dynamic Coordination on Rhodium(II) Axial Sites of Metal-Organic Polyhedra
dc.creator.none.fl_str_mv Sánchez-Fuente, Miguel
Hernández-López, Laura
Maspoch, Daniel
Mas-Ballesté, Rubén
Carné-Sánchez, Arnau
author Sánchez-Fuente, Miguel
author_facet Sánchez-Fuente, Miguel
Hernández-López, Laura
Maspoch, Daniel
Mas-Ballesté, Rubén
Carné-Sánchez, Arnau
author_role author
author2 Hernández-López, Laura
Maspoch, Daniel
Mas-Ballesté, Rubén
Carné-Sánchez, Arnau
author2_role author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Economía y Competitividad (España)
Agencia Estatal de Investigación (España)
Generalitat de Catalunya
Fundación la Caixa
Ministerio de Ciencia e Innovación (España)
European Commission
Maspoch, Daniel [0000-0003-1325-9161]
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv Homogenous catalysis
Ligand exchange
Metal-organic polyhedral
Rh(II) catalysis
Supramolecular surface chemistry
topic Homogenous catalysis
Ligand exchange
Metal-organic polyhedral
Rh(II) catalysis
Supramolecular surface chemistry
description The activity of catalytic nanoparticles is strongly dependent on their surface chemistry, which controls colloidal stability and substrate diffusion toward catalytic sites. In this work, we studied how the outer surface chemistry of nanostructured Rh(II)-based metal-organic cages or polyhedra (Rh-MOPs) impacts their performance in homogeneous catalysis. Specifically, through post-synthetic coordination of aliphatic imidazole ligands onto the exohedral Rh(II) axial sites of Rh-MOPs, we solubilized a cuboctahedral Rh-MOP in dichloromethane, thereby enabling its use as a homogeneous catalyst. We demonstrated that the presence of the coordinating ligand on the surface of the Rh-MOP does not hinder its catalytic activity in styrene aziridination and cyclopropanation reactions, thanks to the dynamic Rh-imidazole coordination bond. Finally, we used similar ligand exchange post-synthetic reactions to develop a ligand-mediated approach for precipitating the Rh-MOP catalyst, facilitating the recovery and reuse of Rh-MOPs as homogeneous catalysts.
publishDate 2024
dc.date.none.fl_str_mv 2024
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/10261/381094
https://api.elsevier.com/content/abstract/scopus_id/85198356157
url http://hdl.handle.net/10261/381094
https://api.elsevier.com/content/abstract/scopus_id/85198356157
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
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info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/RTI2018-095622-B−I00
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-110637RB−I00
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2022-141016OB−I00
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/CEX2021-001214-S
info:eu-repo/grantAgreement/AEI//RYC2020-029749-I
The underlying dataset has been published as supplementary material of the article in the publisher platform at DOI 10.1002/chem.202401661
https://doi.org/10.1002/chem.202401661
Sí
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eu_rights_str_mv openAccess
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dc.publisher.none.fl_str_mv Wiley-VCH
publisher.none.fl_str_mv Wiley-VCH
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