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The Origin of Catalytic Benzylic C−H Oxidation over a Redox‐Active Metal–Organic Framework
Author(s) -
Kimberley Louis,
Sheveleva Alena M.,
Li Jiangnan,
Carter Joseph H.,
Kang Xinchen,
Smith Gemma L.,
Han Xue,
Day Sarah J.,
Tang Chiu C.,
Tuna Floriana,
McInnes Eric J. L.,
Yang Sihai,
Schröder Martin
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202102313
Subject(s) - moiety , redox , electron paramagnetic resonance , catalysis , chemistry , metal , metal organic framework , photochemistry , alcohol oxidation , organic synthesis , inorganic chemistry , organic chemistry , nuclear magnetic resonance , physics , adsorption
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 [Cu 2 II (O 2 CR) 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 t BuOOH (tert‐butyl hydroperoxide) via partial reduction to [Cu II Cu I (O 2 CR) 4 ] species.