Dioxygen Activation by an in situ Reduced CuII Hydrazone Complex1. Issue 24 (20th July 2015)

• Record Type: Journal Article
• Authors: Radunsky, Christian; Kösters, Jutta; Letzel, Matthias C.; Yogendra, Sivathmeehan; Schwickert, Christian; Manck, Sinja; Sarkar, Biprajit; Pöttgen, Rainer; Weigand, Jan J.; Neugebauer, Johannes; Müller, Jens
• Is Part Of: European journal of inorganic chemistry. Issue 24(2015)
• Page Start: 4006
• Page End: 4012
• Publication Date: 2015-07-20
• Subjects: Bioinorganic chemistry -- Oxygen activation -- Copper complexes -- Hydrazones; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201500556
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: 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. Abstract : A Cu II complex of a hydrazone ligand with N, N, S ‐donor functionality is reported that, after in situ reduction, is able to activate dioxygen, leading to a hydroxylation of the ligand and finally resulting in the formation of a Cu II complex of a hydrazone ligand acting as an N, N, O ‐donor.