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- Title
Cooperativity‐Driven Reactivity of a Dinuclear Copper Dimethylglyoxime Complex.
- Authors
Petrikat, Raphael I.; Steiger, Sophie T.; Barani, Elham; Boden, Pit J.; Huber, Maximilian E.; Ringenberg, Mark R.; Niedner‐Schatteburg, Gereon; Fink, Karin; Becker, Sabine
- Abstract
In this report, we present the dinuclear copper(II) dimethylglyoxime (H2dmg) complex [Cu2(H2dmg)(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 H2dmg and thus, facilitates the nucleophilic attack of H2O. This hydrolysis yields butane‐2,3‐dione monoxime (3) and NH2OH that, depending on the solvent, is then either oxidized or reduced. In ethanol, NH2OH is reduced to NH4+, yielding acetaldehyde as the oxidation product. In contrast, in CH3CN, NH2OH is oxidized by CuII to form N2O and [Cu(CH3CN)4]+. Herein are presented the combined synthetic, theoretical, spectroscopic and spectrometric methods that indicate and establish the reaction pathway of this solvent‐dependent reaction.
- Subjects
COPPER compounds; ACETALDEHYDE; LEWIS acidity; COPPER; COOPERATIVE binding (Biochemistry); NITROUS oxide
- Publication
Chemistry - A European Journal, 2023, Vol 29, Issue 22, p1
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.202203438