%0 Journal Article
%A Stüber, Alexander
%A Jurgeleit, Ramona
%A Grimm-Lebsanft, Benjamin
%A Buchenau, Sören
%A Kellner, Ina
%A Appiarius, Yannik
%A Näther, Christian
%A Krahmer, Jan
%A Ivanović-Burmazović, Ivana
%A Rübhausen, Michael
%A Naumova, Maria
%A Tuczek, Felix
%T Dinuclear Copper Complex with a Pyridazine‐Bridged Octadentate Ligand: Monooxygenase Activity and Characterization of Copper‐Oxygen Intermediates
%J Chemistry - a European journal
%V 31
%N 37
%@ 0947-6539
%C Weinheim
%I Wiley-VCH
%M PUBDB-2025-04395
%P e202501659
%D 2025
%X Copper-containing enzymes catalyze the mono-oxygenation of aromatic and aliphatic substrates in nature. Herein, we report on the synthesis of a new dinuclear copper complex supported by an octadentate ligand with a pyridazine backbone. Low-temperature oxygenation leads to a μ-1,1-hydroperoxo dicopper(II) (Cu2OOH) complex, which in turn stoichiometrically converts anthrone (AT) to anthraquinone (AQ). Oxygenation at room temperature, by contrast, leads to a new species that mediates the conversion of AT to AQ in a catalytic fashion, but neither corresponds to a μ-peroxo nor a mono μ-oxo dicopper complex. For further analysis, a μ-hydroxo dicopper(II) (Cu<sub>2</sub>OH) complex is synthesized by oxidation of the copper(I) complex with AgOTf. The electronic and geometric structures of the Cu<sub>2</sub>OOH and Cu<sub>2</sub>OH intermediates, as well as the structure of the room-temperature oxygenation product are elucidated by UV/Vis, Raman, X-ray absorption spectroscopy (XAS), and mass spectrometry, coupled to DFT.
%F PUB:(DE-HGF)16
%9 Journal Article
%$ pmid:40396867
%R 10.1002/chem.202501659
%U https://bib-pubdb1.desy.de/record/639294