Stüber Alexander, Jurgeleit Ramona, Grimm-Lebsanft Benjamin, Buchenau Sören, Kellner Ina, Appiarius Yannik, Näther Christian, Krahmer Jan, Ivanović-Burmazović Ivana, Rübhausen Michael, Naumova Maria A, Tuczek Felix
Institute of Inorganic Chemistry, Christian-Albrechts-University of Kiel, Max-Eyth-Straße 2, 24118, Kiel, Germany.
Institut für Nanostruktur- und Festkörperphysik, Center for Free Electron Laser Science (CFEL), Universität Hamburg, Luruper Chaussee 149, 22761, Hamburg, Germany.
Chemistry. 2025 Jul 2;31(37):e202501659. doi: 10.1002/chem.202501659. Epub 2025 Jun 3.
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) (CuOOH) 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) (CuOH) complex is synthesized by oxidation of the copper(I) complex with AgOTf. The electronic and geometric structures of the CuOOH and CuOH 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.
含铜酶在自然界中催化芳香族和脂肪族底物的单加氧反应。在此，我们报道了一种由具有哒嗪骨架的八齿配体支撑的新型双核铜配合物的合成。低温氧化生成一种μ-1,1-氢过氧双核铜（II）（CuOOH）配合物，该配合物继而化学计量地将蒽酮（AT）转化为蒽醌（AQ）。相比之下，室温下的氧化生成一种新物种，该物种以催化方式介导AT向AQ的转化，但既不对应于μ-过氧也不对应于单μ-氧双核铜配合物。为了进一步分析，通过用AgOTf氧化铜（I）配合物合成了一种μ-羟基双核铜（II）（CuOH）配合物。通过紫外/可见光谱、拉曼光谱、X射线吸收光谱（XAS）和质谱，并结合密度泛函理论（DFT），阐明了CuOOH和CuOH中间体的电子和几何结构，以及室温氧化产物的结构。
