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A fluxional CuNO core: Binding of a keto oxygen atom to Cu and Ag

European Journal of Inorganic Chemistry, ISSN: 1434-1948, Vol: 2005, Issue: 23, Page: 4834-4839
2005
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[Cu(2-acetylpyridine)]ClO (1), characterised here, has a novel CuNO core in the solid state. Variable-temperature H NMR studies show that the two chelate rings open up in solution at room temperature and the keto oxygen atoms dangle freely. As the temperature is lowered, the O atoms tend to bind to the metal atom. The corresponding silver(I) complex, [Ag(2-acetylpyridine)]ClO (4), characterised by single-crystal X-ray crystallography, has an AgN core in the solid state as well as in solution. Thus, while 1 is fluxional, 4 is not. In cyclic voltammetry, complex 1 displays a quasireversible Cu couple with a half-wave potential of 0.40 V vs. SCE. Complex 1 is easily oxidised by air and HO in methanol to give rise to a dinuclear copper(II) complex where the ligand framework is not simple acetylpyridine. © Wiley-VCH Verlag GmbH & Co. KGaA, 2005.

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