In:
Chemistry – A European Journal, Wiley, Vol. 29, No. 22 ( 2023-04-18)
Abstract:
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.
Type of Medium:
Online Resource
ISSN:
0947-6539
,
1521-3765
DOI:
10.1002/chem.202203438
Language:
English
Publisher:
Wiley
Publication Date:
2023
detail.hit.zdb_id:
1478547-X
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