%0 Journal Article
%A Jurgeleit, Ramona
%A Grimm-Lebsanft, Benjamin
%A Flöser, Benedikt Maria
%A Teubner, Melissa
%A Buchenau, Soeren
%A Senft, Laura
%A Hoffmann, Jonas
%A Naumova, Maria
%A Näther, Christian
%A Ivanović-Burmazović, Ivana
%A Rübhausen, Michael
%A Tuczek, Felix
%T Catalytic Oxygenation of Hydrocarbons by Mono‐μ‐oxo Dicopper(II) Species Resulting from O−O Cleavage of Tetranuclear Cu I /Cu II Peroxo Complexes
%J Angewandte Chemie / International edition
%V 60
%N 25
%@ 1521-3773
%C Weinheim
%I Wiley-VCH
%M PUBDB-2021-03519
%P 14154-14162
%D 2021
%X One of the challenges of catalysis is the transformation of inert C−H bonds to useful products. Copper-containing monooxygenases play an important role in this regard. Here we show that low-temperature oxygenation of dinuclear copper(I) complexes leads to unusual tetranuclear, mixed-valent μ<sub>4</sub>-peroxo [Cu<sup>I</sup>/Cu<sup>II</sup>]<sub>2</sub> complexes. These Cu<sub>4</sub>O<sub>2</sub> intermediates promote irreversible and thermally activated O−O bond homolysis, generating Cu<sub>2</sub>O complexes that catalyze strongly exergonic H-atom abstraction from hydrocarbons, coupled to O-transfer. The Cu<sub>2</sub>O species can also be produced with N<sub>2</sub>O, demonstrating their capability for small-molecule activation. The binding and cleavage of O<sub>2</sub> leading to the primary Cu<sub>4</sub>O<sub>2</sub> intermediate and the Cu<sub>2</sub>O complexes, respectively, is elucidated with a range of solution spectroscopic methods and mass spectrometry. The unique reactivities of these species establish an unprecedented, 100 
%F PUB:(DE-HGF)16
%9 Journal Article
%$ pmid:33856088
%U <Go to ISI:>//WOS:000648053600001
%R 10.1002/anie.202101035
%U https://bib-pubdb1.desy.de/record/462678