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

Jurgeleit R, Grimm-Lebsanft B, Floeser BM, Teubner M, Buchenau S, Senft L, Hoffmann J, Naumova M, Naether C, Ivanovic-Burmazovic I, Ruebhausen M, Tuczek F (2021)

Publication Type: Journal article

Publication year: 2021

Journal

Angewandte Chemie International Edition Wiley

DOI: 10.1002/anie.202101035

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 mu(4)-peroxo [Cu-I/Cu-II](2) complexes. These Cu4O2 intermediates promote irreversible and thermally activated O-O bond homolysis, generating Cu2O complexes that catalyze strongly exergonic H-atom abstraction from hydrocarbons, coupled to O-transfer. The Cu2O species can also be produced with N2O, demonstrating their capability for small-molecule activation. The binding and cleavage of O-2 leading to the primary Cu4O2 intermediate and the Cu2O 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.

Authors with CRIS profile

Laura Senft Lehrstuhl für Anorganische und Allgemeine Chemie Ivana Ivanovic-Burmazovic Lehrstuhl für Bioanorganische Chemie

Involved external institutions

Christian-Albrechts-Universität zu Kiel DE Germany (DE) Universität Hamburg (UHH) DE Germany (DE) Universität Bremen DE Germany (DE) Deutsches Elektronen-Synchrotron DESY DE Germany (DE)

How to cite

APA:

Jurgeleit, R., Grimm-Lebsanft, B., Floeser, B.M., Teubner, M., Buchenau, S., Senft, L.,... Tuczek, F. (2021). Catalytic Oxygenation of Hydrocarbons by Mono-mu-oxo Dicopper(II) Species Resulting from O-O Cleavage of Tetranuclear Cu-I/Cu-II Peroxo Complexes. Angewandte Chemie International Edition. https://dx.doi.org/10.1002/anie.202101035

MLA:

Jurgeleit, Ramona, et al. "Catalytic Oxygenation of Hydrocarbons by Mono-mu-oxo Dicopper(II) Species Resulting from O-O Cleavage of Tetranuclear Cu-I/Cu-II Peroxo Complexes." Angewandte Chemie International Edition (2021).

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