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The origin of catalytic benzylic C‐H oxidation over a redox‐active metal‐organic framework

DOI: 10.1002/anie.202102313 DOI Help

Authors: Martin Schroeder (University of Manchester) , Louis Kimberley (University of Manchester) , Alena M. Sheveleva (University of Manchester) , Jiangnan Li (University of Manchester) , Joseph H. Carter (University of Manchester) , Xinchen Kang (University of Manchester) , Gemma L. Smith (University of Manchester) , Xue Han (University of Manchester) , Sarah J. Day (Diamond Light Source) , Chiu C. Tang (Diamond Light Source) , Floriana Tuna (University of Manchester) , Eric J. L. Mcinnes (University of Manchester) , Sihai Yang (University of Manchester)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Angewandte Chemie International Edition

State: Published (Approved)
Published: April 2021

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 metals catalysts. Here, 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 (t‐butyl hydroperoxide) via partial reduction to [CuIICuI(O2CR)4] species.

Journal Keywords: metal-organic framework; catalysis; benzylic oxidation; EPR

Subject Areas: Chemistry


Instruments: I11-High Resolution Powder Diffraction

Discipline Tags:

Catalysis Physical Chemistry Material Sciences Metallurgy Metal-Organic Frameworks Chemistry Organometallic Chemistry

Technical Tags:

Diffraction X-ray Powder Diffraction