TY  - JOUR
AU  - Stüber, Alexander
AU  - Jurgeleit, Ramona
AU  - Grimm-Lebsanft, Benjamin
AU  - Buchenau, Sören
AU  - Kellner, Ina
AU  - Appiarius, Yannik
AU  - Näther, Christian
AU  - Krahmer, Jan
AU  - Ivanović-Burmazović, Ivana
AU  - Rübhausen, Michael
AU  - Naumova, Maria
AU  - Tuczek, Felix
TI  - Dinuclear Copper Complex with a Pyridazine‐Bridged Octadentate Ligand: Monooxygenase Activity and Characterization of Copper‐Oxygen Intermediates
JO  - Chemistry - a European journal
VL  - 31
IS  - 37
SN  - 0947-6539
CY  - Weinheim
PB  - Wiley-VCH
M1  - PUBDB-2025-04395
SP  - e202501659
PY  - 2025
AB  - 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. 
LB  - PUB:(DE-HGF)16
C6  - pmid:40396867
DO  - DOI:10.1002/chem.202501659
UR  - https://bib-pubdb1.desy.de/record/639294
ER  -