Some copper(II) and nickel(II) amine-cyanide derivatives. II. Some crystalline derivatives

Abstract

The preparations and properties of the compounds Cu(A)]₂CN(ClO4)₃, M(tet α)CNClO₄, and Ni(tet α)(CN)₂ are described, where [Cu(A)]²⁺ is a cyclic tetradentate Schiff base-amine complex (hexamethyltetraazacyclotetradeoadiene- copper(11) formed by condensation of bisethylenediaminecopper(11) with acetone), and where [M(tet α)]²⁺ is the copper(11) or nicke1(11) complex of the cyclic tetramine (hexamethyltetraazaoyclotetradecane) formed by reduction of the [M(A)]²⁺ complex. From consideration of the infrared and metal ion spectra, it is concluded that the [Cu(A)]²⁺ compound has a dimeric structure with bridging cyanide ions and five-coordinate copper(11) ions, that the two monocyanide adducts have six-coordinate polymeric structures with bridging cyanide ions, and that Ni(tet α)(CN)₂ has a six-coordinate structure with terminal cyanide ions. The copper compounds are the first reported stable, crystalline compounds with cyanide coordinated to copper(11).