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Dioxygen Activation by an in situ Reduced Cu II Hydrazone Complex
Author(s) -
Radunsky Christian,
Kösters Jutta,
Letzel Matthias C.,
Yogendra Sivathmeehan,
Schwickert Christian,
Manck Sinja,
Sarkar Biprajit,
Pöttgen Rainer,
Weigand Jan J.,
Neugebauer Johannes,
Müller Jens
Publication year - 2015
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201500556
Subject(s) - hydrazone , chemistry , moiety , ligand (biochemistry) , metal , copper , catalysis , reactivity (psychology) , stereochemistry , crystal structure , methanol , combinatorial chemistry , photochemistry , crystallography , organic chemistry , medicine , biochemistry , receptor , alternative medicine , pathology
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 β position (C–H → C–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.