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Zur Stabilität und Struktur der CuI-Komplexe des Imidazols und Histamins. Chemie des einwertigen Kupfers in homogener, polarer Lösung. 1. Mitteilung

✍ Scribed by C. Sigwart; P. Kroneck; P. Hemmerich


Publisher
John Wiley and Sons
Year
1970
Tongue
German
Weight
419 KB
Volume
53
Category
Article
ISSN
0018-019X

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✦ Synopsis


Abstract

Univalent copper is stabilized in aqueous medium by the non‐protophilic ligand CH~3~CN, allowing ligand displacement reactions to be investigated as if a stable Cu^I^‐hydrate did exist. Under these conditions the formation of Cu^I^‐complexes with imidazole and its derivatives has been studied in polar solution in the absence of Cu^II^. Imidazole (ImH) acts upon Cu^I^ as a bidentate ligand forming polynuclear chains according to the equation
equation image

Histamine reacts in the same way, i. e. the coordination number of Cu^I^ does not exceed 2; by comparison of the complexes of Cu^I^ with histamine and its N‐methyl‐derivatives it is shown that no six‐membered chelate – which sterically would be possible – is built up. Trigonal as well as tetrahedral coordination of Cu^I^ – i. e. chelate formation – in dilute polar solutions are confined to π‐ or d‐acceptor ligands, e. g. bipyridine or methionine. Conclusions are drawn from this on the requirements for redox‐active copper in proteins.