Journal Article

PUBDB-2021-03519

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Catalytic Oxygenation of Hydrocarbons by Mono‐μ‐oxo Dicopper(II) Species Resulting from O−O Cleavage of Tetranuclear Cu I /Cu II Peroxo Complexes

Jurgeleit, R. ; Grimm-Lebsanft, B.Extern* ; Flöser, B. M. ; Teubner, M.CFEL*Extern* ; Buchenau, S.Extern* ; Senft, L. ; Hoffmann, J. ; Naumova, M.XFEL.EU*DESY* ; Näther, C. ; Ivanović-Burmazović, I. ; Rübhausen, M. (Corresponding author) ; Tuczek, F. (Corresponding author)Extern*

2021
Wiley-VCH Weinheim

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Please use a persistent id in citations: doi:10.1002/anie.202101035  doi:10.3204/PUBDB-2021-03519

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 $μ_4$-peroxo [Cu$^I$/Cu$^{II}$]$_2$ complexes. These Cu$_4$O$_2$ intermediates promote irreversible and thermally activated O−O bond homolysis, generating Cu$_2$O complexes that catalyze strongly exergonic H-atom abstraction from hydrocarbons, coupled to O-transfer. The Cu$_2$O species can also be produced with N$_2$O, demonstrating their capability for small-molecule activation. The binding and cleavage of O$_2$ leading to the primary Cu$_4$O$_2$ intermediate and the Cu$_2$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 O$_2$.

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Contributing Institute(s):

1. DOOR-User (DOOR ; HAS-User)
2. Institute of Nanostructure and Solid State Physics (UNI/INF)
3. Uni Kiel (UKiel)

Research Program(s):

1. 632 - Materials – Quantum, Complex and Functional Materials (POF4-632) (POF4-632)
2. 6G3 - PETRA III (DESY) (POF4-6G3) (POF4-6G3)

Experiment(s):

1. PETRA Beamline P65 (PETRA III)
2. PETRA Beamline P64 (PETRA III)

Appears in the scientific report 2021

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Database coverage:
; ; ; Chemical Reactions ; Clarivate Analytics Master Journal List ; Current Contents - Life Sciences ; Current Contents - Physical, Chemical and Earth Sciences ; DEAL Wiley ; Ebsco Academic Search ; Essential Science Indicators ; IF >= 10 ; Index Chemicus ; JCR ; Nationallizenz ; SCOPUS ; Science Citation Index Expanded ; Web of Science Core Collection

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