TY  - JOUR
AU  - Jurgeleit, Ramona
AU  - Grimm-Lebsanft, Benjamin
AU  - Flöser, Benedikt Maria
AU  - Teubner, Melissa
AU  - Buchenau, Soeren
AU  - Senft, Laura
AU  - Hoffmann, Jonas
AU  - Naumova, Maria
AU  - Näther, Christian
AU  - Ivanović-Burmazović, Ivana
AU  - Rübhausen, Michael
AU  - Tuczek, Felix
TI  - Catalytic Oxygenation of Hydrocarbons by Mono‐μ‐oxo Dicopper(II) Species Resulting from O−O Cleavage of Tetranuclear Cu I /Cu II Peroxo Complexes
JO  - Angewandte Chemie / International edition
VL  - 60
IS  - 25
SN  - 1521-3773
CY  - Weinheim
PB  - Wiley-VCH
M1  - PUBDB-2021-03519
SP  - 14154-14162
PY  - 2021
AB  - 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 
LB  - PUB:(DE-HGF)16
C6  - pmid:33856088
UR  - <Go to ISI:>//WOS:000648053600001
DO  - DOI:10.1002/anie.202101035
UR  - https://bib-pubdb1.desy.de/record/462678
ER  -