Catalytic Hydrogenolysis of Aryl C-F Bonds Using a Bimetallic Rhodium-Indium Complex
- 8 July 2020
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 142 (27), 11641-11646
- https://doi.org/10.1021/jacs.0c04937
Abstract
A homogeneous rhodium-indium catalyst hydrodefluorinates substrates bearing strong aryl C-F bonds, including difluoro- and fluorobenzene, using 1 atm of H-2, alkoxide bases, and moderate temperatures (70-90 degrees C). Characterization of catalytic intermediates establishes a formal Rh-I/Rh-I redox cycle. The Rh -> In interaction is proposed to enable catalysis by stabilizing the reactive Rh--(I) species, which is responsible for cleaving the Ar-F bond and is ultimately regenerated using H-2 and base.Funding Information
- Division of Chemistry (1800110)
This publication has 70 references indexed in Scilit:
- Selectively catalytic hydrodefluorination of perfluoroarenes by Co(PMe3)4 with sodium formate as reducing agent and mechanism studyDalton Transactions, 2013
- Complete Hydrodehalogenation of Polyfluorinated and Other Polyhalogenated Benzenes under Mild Catalytic ConditionsEnvironmental Science & Technology, 2013
- Synthesis of Rhodaboratranes Bearing Phosphine-Tethered Boranes: Evaluation of the Metal–Boron InteractionOrganometallics, 2012
- A Highly Reactive Rhodium(I)–Boryl Complex as a Useful Tool for C-H Bond Activation and Catalytic C-F Bond BorylationAngewandte Chemie, 2010
- Sequential C–F activation and borylation of fluoropyridines via intermediate Rh(i) fluoropyridyl complexes: a multinuclear NMR investigationChemical Communications, 2007
- A Simple Description of the Bonding in Transition-Metal Borane ComplexesOrganometallics, 2006
- Deprotonation of the Transition Metal Hydride (η5-C5Me5)(PMe3)IrH2. Synthesis and Chemistry of the Strongly Basic Lithium Iridate (η5-C5Me5)(PMe3)Ir(H)(Li)Organometallics, 1999
- Synthesis and Characterization of Hydrotris(pyrazolyl)borate Dihydrogen/Hydride Complexes of Rhodium and IridiumJournal of the American Chemical Society, 1997
- Selectivity in the activation of fluorinated aromatic hydrocarbons by rhodium complexes [(C5H5)Rh(PMe3)] and [(C5Me5)Rh(PMe3)]Organometallics, 1994
- Solvation and ion pairing of alkali-metal alkoxides in dimethyl sulfoxide. Conductometric studiesJournal of the American Chemical Society, 1974