Dioxygen Activation by an in situ Reduced Cu-II Hydrazone Complex

作者：Radunsky Christian; Koesters Jutta; Letzel Matthias C; Yogendra Sivathmeehan; Schwickert Christian; Manck Sinja; Sarkar Biprajit; Poettgen Rainer; Weigand Jan J; Neugebauer Johannes; Mueller Jens

来源：European Journal of Inorganic Chemistry, 2015, 2015(24): 4006-4012.

DOI：10.1002/ejic.201500556

• Bioinorganic chemistry
• Oxygen activation
• Copper complexes
• Hydrazones

A Cu-II hydrazone complex has been synthesized that can be reduced in situ in boiling methanol to give the corresponding Cu-I complex. The latter complex readily activates dioxygen under ambient conditions, as was unambiguously shown by isotopic labeling studies. As a consequence of the dioxygen activation, the thienyl moiety appended to the hydrazone ligand is easily oxidized in position (C-HC-O), finally leading to a change in the coordination environment of the central metal ion. All relevant complexes have been structurally characterized by single-crystal X-ray diffraction analyses. The hydrazone ligand applied in this study does not mimic a biologically relevant coordination motif in copper-containing oxygenases. Nonetheless, the reactivity of the Cu-I complex resembles that found in many oxygenases, indicating that hydrazone ligands may be well-suited for the generation of novel bioinspired oxidation catalysts.

• 出版日期2015-8