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. 2023 Apr 18;29(22):e202203438.
doi: 10.1002/chem.202203438. Epub 2023 Mar 20.

Cooperativity-Driven Reactivity of a Dinuclear Copper Dimethylglyoxime Complex

Raphael I Petrikat  1 , Sophie T Steiger  2 , Elham Barani  3 , Pit J Boden  2 , Maximilian E Huber  2 , Mark R Ringenberg  4 , Gereon Niedner-Schatteburg  2 , Karin Fink  3 , Sabine Becker  1
Affiliations

Cooperativity-Driven Reactivity of a Dinuclear Copper Dimethylglyoxime Complex

Raphael I Petrikat et al. Chemistry. .

Abstract

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 CuII 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.

Keywords: cooperative effects; copper complexes; dimethyglyoxime; hydrolysis; hydroxylamine.

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