1 research outputs found
Cooperativity‐Driven Reactivity of a Dinuclear Copper Dimethylglyoxime Complex
In this report, we present the dinuclear copper(II) dimethylglyoxime (Hdmg) complex [Cu(Hdmg)(Hdmg)(dmg)] (1), which, in contrast to its mononuclear analogue [Cu(Hdmg)] (2), is subject to a cooperativity-driven hydrolysis. The combined Lewis acidity of both copper centers increases the electrophilicity of the carbon atom in the bridging μ-O−N=C-group of Hdmg and thus, facilitates the nucleophilic attack of H2O. This hydrolysis yields butane-2,3-dione monoxime (3) and NHOH that, depending on the solvent, is then either oxidized or reduced. In ethanol, NHOH is reduced to NH, yielding acetaldehyde as the oxidation product. In contrast, in CHCN, NHOH is oxidized by Cu to form NO and [Cu(CHCN)4]. Herein are presented the combined synthetic, theoretical, spectroscopic and spectrometric methods that indicate and establish the reaction pathway of this solvent-dependent reaction