Recyclable Homogeneous Catalysis Enabled by Dynamic Coordination on Rhodium(II) Axial Sites of Metal-Organic Polyhedra
Sánchez-Fuente, Miguel (Universidad Autónoma de Madrid)
Hernández López, Laura (Universitat Autònoma de Barcelona. Departament de Química)
Maspoch Comamala, Daniel (Institut Català de Nanociència i Nanotecnologia)
Mas-Ballesté, Rubén (Universidad Autónoma de Madrid)
Carné-Sánchez, Arnau (Universitat Autònoma de Barcelona. Departament de Química)

Date:	2024
Abstract:	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.
Grants:	Agencia Estatal de Investigación RTI2018-095622-B-I00 Agencia Estatal de Investigación PID2019-110637RB-I00 Agencia Estatal de Investigación PID2022-141016OB-I00 Agència de Gestió d'Ajuts Universitaris i de Recerca 2021/SGR-00458 "la Caixa" Foundation 100010434 Agencia Estatal de Investigación CEX2021-001214-S Agencia Estatal de Investigación RYC2020-029749-I Agencia Estatal de Investigación PRE2019-088056 Agencia Estatal de Investigación PRE2020-092295
Rights:	Aquest document està subjecte a una llicència d'ús Creative Commons. Es permet la reproducció total o parcial, la distribució, la comunicació pública de l'obra i la creació d'obres derivades, sempre que no sigui amb finalitats comercials, i sempre que es reconegui l'autoria de l'obra original.
Language:	Anglès
Document:	Article ; recerca ; Versió publicada
Published in:	Chemistry (Weinheim), Vol. 30, Issue 43 (August 2024) , art. e202401661, ISSN 1521-3765

DOI: 10.1002/chem.202401661

6 p, 1.6 MB

The record appears in these collections:
Research literature > UAB research groups literature > Research Centres and Groups (research output) > Experimental sciences > Catalan Institute of Nanoscience and Nanotechnology (ICN2)
Articles > Research articles
Articles > Published articles