The Origin of Catalytic Benzylic C−H Oxidation over a Redox‐Active Metal–Organic Framework
Open Access
- 13 April 2021
- journal article
- research article
- Published by Wiley in Angewandte Chemie International Edition
- Vol. 60 (28) , 15243-15247
Abstract
Selective oxidation of benzylic C−H compounds to ketones is important for the production of a wide range of fine chemicals, and is often achieved using toxic or precious metal catalysts. Herein, we report the efficient oxidation of benzylic C−H groups in a broad range of substrates under mild conditions over a robust metal–organic framework material, MFM‐170, incorporating redox‐active [Cu2II(O2CR)4] paddlewheel nodes. A comprehensive investigation employing electron paramagnetic resonance (EPR) spectroscopy and synchrotron X‐ray diffraction has identified the critical role of the paddlewheel moiety in activating the oxidant tBuOOH (tert‐butyl hydroperoxide) via partial reduction to [CuIICuI(O2CR)4] species.Keywords
Funding Information
- Engineering and Physical Sciences Research Council (EP/I011870)
- H2020 European Research Council (742401)
This publication has 36 references indexed in Scilit:
- Tuneable nature of metal organic frameworks as heterogeneous solid catalysts for alcohol oxidationChemical Communications, 2017
- Kinetically controlled synthesis of two-dimensional Zr/Hf metal–organic framework nanosheets via a modulated hydrothermal approachJournal of Materials Chemistry A, 2017
- One-pot tandem catalysis over Pd@MIL-101: boosting the efficiency of nitro compound hydrogenation by coupling with ammonia borane dehydrogenationChemical Communications, 2015
- The Chemistry and Applications of Metal-Organic FrameworksScience, 2013
- Selective Palladium‐Loaded MIL‐101 CatalystsChemistry – A European Journal, 2011
- Porous Chromium Terephthalate MIL‐101 with Coordinatively Unsaturated Sites: Surface Functionalization, Encapsulation, Sorption and CatalysisAdvanced Functional Materials, 2009
- Amine Grafting on Coordinatively Unsaturated Metal Centers of MOFs: Consequences for Catalysis and Metal EncapsulationAngewandte Chemie International Edition, 2008
- MOFs as catalysts: Activity, reusability and shape-selectivity of a Pd-containing MOFJournal of Catalysis, 2007
- Copper-catalyzed homolytic and heterolytic benzylic and allylic oxidation using tert-butyl hydroperoxideJournal of the Chemical Society, Perkin Transactions 2, 1998
- Handbook of Heterogeneous Catalysis1997