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

SUBMITTER: Jurgeleit R 

PROVIDER: S-EPMC8251984 | biostudies-literature | 2021 Jun

REPOSITORIES: biostudies-literature