Cooperativity-Driven Reactivity of a Dinuclear Copper Dimethylglyoxime Complex.

Autor: Petrikat RI; RPTU Kaiserslautern-Landau, Institut für Anorganische Chemie, Erwin-Schroedinger-Str. 54, 67663, Kaiserslautern, Germany., Steiger ST; RPTU Kaiserslautern-Landau, Institut für Physikalische Chemie, Erwin-Schroedinger-Str. 52, 67663, Kaiserslautern, Germany., Barani E; Karlsruhe Institute of Technology (KIT), Institute of Nanotechnology, Hermann-von-Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany., Boden PJ; RPTU Kaiserslautern-Landau, Institut für Physikalische Chemie, Erwin-Schroedinger-Str. 52, 67663, Kaiserslautern, Germany., Huber ME; RPTU Kaiserslautern-Landau, Institut für Physikalische Chemie, Erwin-Schroedinger-Str. 52, 67663, Kaiserslautern, Germany., Ringenberg MR; Société Suisse des Explosifs, Fabrikstrasse 48, CH-3900, Brig, Switzerland., Niedner-Schatteburg G; RPTU Kaiserslautern-Landau, Institut für Physikalische Chemie, Erwin-Schroedinger-Str. 52, 67663, Kaiserslautern, Germany., Fink K; Karlsruhe Institute of Technology (KIT), Institute of Nanotechnology, Hermann-von-Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany., Becker S; RPTU Kaiserslautern-Landau, Institut für Anorganische Chemie, Erwin-Schroedinger-Str. 54, 67663, Kaiserslautern, Germany.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2023 Apr 18; Vol. 29 (22), pp. e202203438. Date of Electronic Publication: 2023 Mar 20.
DOI: 10.1002/chem.202203438
Abstrakt: In this report, we present the dinuclear copper(II) dimethylglyoxime (H 2 dmg) complex [Cu 2 (H 2 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 μ 2 -O-N=C-group of H 2 dmg and thus, facilitates the nucleophilic attack of H 2 O. This hydrolysis yields butane-2,3-dione monoxime (3) and NH 2 OH that, depending on the solvent, is then either oxidized or reduced. In ethanol, NH 2 OH is reduced to NH 4 + , yielding acetaldehyde as the oxidation product. In contrast, in CH 3 CN, NH 2 OH is oxidized by Cu II to form N 2 O and [Cu(CH 3 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.
(© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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