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

Autor: Sánchez-Fuente M; Department of Inorganic Chemistry (Module 7), Facultad de Ciencias, Universidad Autónoma de Madrid, Madrid, 28049, Spain., Hernández-López L; Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and The Barcelona Institute of Science and Technology, Campus UAB, Bellaterra, Barcelona, 08193, Spain.; Departament de Química, Facultat de Ciencies, Universitat Autonoma de Barcelona, Bellaterra, 08193, Spain., Maspoch D; Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and The Barcelona Institute of Science and Technology, Campus UAB, Bellaterra, Barcelona, 08193, Spain.; Departament de Química, Facultat de Ciencies, Universitat Autonoma de Barcelona, Bellaterra, 08193, Spain.; ICREA, Pg. Lluís Companys 23, 08010, Barcelona, Spain., Mas-Ballesté R; Department of Inorganic Chemistry (Module 7), Facultad de Ciencias, Universidad Autónoma de Madrid, Madrid, 28049, Spain.; Institute for Advanced Research in Chemical Sciences (IAdChem), Universidad Autónoma de Madrid, Madrid, 28049, Spain., Carné-Sánchez A; Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and The Barcelona Institute of Science and Technology, Campus UAB, Bellaterra, Barcelona, 08193, Spain.; Departament de Química, Facultat de Ciencies, Universitat Autonoma de Barcelona, Bellaterra, 08193, Spain.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2024 Aug 01; Vol. 30 (43), pp. e202401661. Date of Electronic Publication: 2024 Jul 15.
DOI: 10.1002/chem.202401661
Abstrakt: 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.
(© 2024 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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