Dataset Information

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 .

SUBMITTER: Jurgeleit R

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

REPOSITORIES: biostudies-literature

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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.

Jurgeleit Ramona R Grimm-Lebsanft Benjamin B Flöser Benedikt Maria BM Teubner Melissa M Buchenau Sören S Senft Laura L Hoffmann Jonas J Naumova Maria M Näther Christian C Ivanović-Burmazović Ivana I Rübhausen Michael M Tuczek Felix F

Angewandte Chemie (International ed. in English) 20210507 25

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 Cu<s ...[more]

PMID: 33856088

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Dataset Information

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

Publications

Catalytic Oxygenation of Hydrocarbons by Mono-μ-oxo Dicopper(II) Species Resulting from O-O Cleavage of Tetranuclear Cu<sup>I</sup> /Cu<sup>II</sup> Peroxo Complexes.

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