Catalytic Oxygenation of Hydrocarbons by Mono‐μ‐oxo Dicopper(II) Species Resulting from O−O Cleavage of Tetranuclear Cu I /Cu II Peroxo Complexes

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Abstract
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 .
Funding Information
  • Deutsche Forschungsgemeinschaft (05K19GU5)

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