Reactions of Sodium N,N-Diethyldithiocarbamate and Potassium Ethyl Xanthate with some 3d Transition Metal Halides in the presence of 2,2′-Bipyridyl and 1,10-Phenanthroline

Abstract

The synthesis and some properties of ethylxanthate (Xan⁻) complexes, MXan₂ and MXan₃⁻ (M = manganese(II) and iron(II)) are reported. Reactions between divalent metal halides (manganese, iron, cobalt, nickel, copper, and zinc) and Xan⁻ and between the metal halides and N,N-diethyldithiocarbamate (dtc⁻) in the presence of nitrogen bases 1,10-phenanthroline (phen) and 2,2′-bipyridyl (bipy) are described. The major products of these reactions are complexes of the type MXan₂.Base and Mdtc₂.Base (with notable exceptions). In the former series with bipy, two different crystalline modifications of the manganese, iron, and cobalt complexes are formed, and copper(II) is reduced to copper(I) by Xan⁻ in the presence of both bases. In the nickel–dtc system with bipy, Nidtc₂ is produced, while with phen, the complex [Niphen₃]dtc₂ is formed. The latter reacts very rapidly with methylene chloride. Cudtc₂ is produced from the copper(II)/base/dtc reactions.