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Catalytic Oxygenation of Hydrocarbons by Mono‐μ‐oxo Dicopper(II) Species Resulting from O−O Cleavage of Tetranuclear Cu I /Cu II Peroxo Complexes
Author(s) -
Jurgeleit Ramona,
GrimmLebsanft Benjamin,
Flöser Benedikt Maria,
Teubner Melissa,
Buchenau Sören,
Senft Laura,
Hoffmann Jonas,
Naumova Maria,
Näther Christian,
IvanovićBurmazović Ivana,
Rübhausen Michael,
Tuczek Felix
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.202101035
Subject(s) - catalysis , chemistry , copper , bond cleavage , homolysis , exergonic reaction , photochemistry , medicinal chemistry , dissociation (chemistry) , stereochemistry , radical , organic chemistry
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 4 ‐peroxo [Cu I /Cu II ] 2 complexes. These Cu 4 O 2 intermediates promote irreversible and thermally activated O−O bond homolysis, generating Cu 2 O complexes that catalyze strongly exergonic H‐atom abstraction from hydrocarbons, coupled to O‐transfer. The Cu 2 O species can also be produced with N 2 O, demonstrating their capability for small‐molecule activation. The binding and cleavage of O 2 leading to the primary Cu 4 O 2 intermediate and the Cu 2 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 % atom‐economic scenario for the catalytic, copper‐mediated monooxygenation of organic substrates, employing both O‐atoms of O 2 .