Cooperativity-Driven Reactivity of a Dinuclear Copper Dimethylglyoxime Complex

In this report, we present the dinuclear copper(II) dimethylglyoxime (H₂ dmg) complex [Cu₂ (H₂ dmg)(Hdmg)(dmg)]⁺ (1), which, in contrast to its mononuclear analogue [Cu(Hdmg)₂ ] (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 μ₂ -O-N=C-group of H₂ dmg and thus, facilitates the nucleophilic attack of H₂ O. This hydrolysis yields butane-2,3-dione monoxime (3) and NH₂ OH that, depending on the solvent, is then either oxidized or reduced. In ethanol, NH₂ OH is reduced to NH₄ ⁺ , yielding acetaldehyde as the oxidation product. In contrast, in CH₃ CN, NH₂ OH is oxidized by Cu^II to form N₂ O and [Cu(CH₃ CN)₄ ]⁺ . Herein are presented the combined synthetic, theoretical, spectroscopic and spectrometric methods that indicate and establish the reaction pathway of this solvent-dependent reaction.