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

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 μ₄ -peroxo [Cu^I /Cu^II ]₂ complexes. These Cu₄ O₂ intermediates promote irreversible and thermally activated O-O bond homolysis, generating Cu₂ O complexes that catalyze strongly exergonic H-atom abstraction from hydrocarbons, coupled to O-transfer. The Cu₂ O species can also be produced with N₂ O, demonstrating their capability for small-molecule activation. The binding and cleavage of O₂ leading to the primary Cu₄ O₂ intermediate and the Cu₂ 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 O₂ .