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Catalytic Oxygenation of Hydrocarbons by Mono-μ-oxo Dicopper(II) Species Resulting from O-O Cleavage of Tetranuclear CuI /CuII Peroxo Complexes.

Ramona JurgeleitBenjamin Grimm-LebsanftBenedikt Maria FlöserMelissa TeubnerSören BuchenauLaura SenftJonas HoffmannMaria NaumovaChristian NätherIvana Ivanovic-BurmazovicMichael RübhausenFelix Tuczek
Published in: Angewandte Chemie (International ed. in English) (2021)
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 [CuI /CuII ]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 .
Keyphrases
  • small molecule
  • aqueous solution
  • metal organic framework
  • dna binding
  • molecular dynamics
  • electron transfer
  • oxide nanoparticles
  • liquid chromatography