From Wiley via Jisc Publications RouterHistory: received 2021-02-15, rev-recd 2021-03-27, pub-electronic 2021-06-04Article version: VoRPublication status: PublishedFunder: Engineering and Physical Sciences Research Council; Id: http://dx.doi.org/10.13039/501100000266; Grant(s): EP/I011870Funder: H2020 European Research Council; Id: http://dx.doi.org/10.13039/100010663; Grant(s): 742401Abstract: 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
