Electron spin resonance study of the copper(II) chelates of certain thio ligands

Abstract

Electron spin resonance measurements have been made on the copper(II) chelates of o-methylmercaptobenzoic acid, S-carboxydiethyldithiocarbamic acid, thiazolidine-4-carboxylic acid, 5-hydroxy-1,3-benzoxathiol-2-one and diacetyl bisthiosemicarbazone. The e.s.r. spectra of dimethylformamide solutions of the chelates have been interpreted in terms of dimeric species which are believed to exist at room temperature, as well as in frozen solutions in the case of o-methyl-mercaptobenzoic acid, S-carboxydiethyldithiocarbamic acid, and 5-hydroxy-1,3-benzoxathiol-2-one, whereas the dimeric forms of the remaining chelates are formed solely in frozen solution. The results have been interpreted as arising from dipole-dipole coupling between the copper(II) ions in their dimeric forms, and a line simulation procedure employed to extract the distance between the copper(II) dipoles. This information has been used to suggest the possible structures of the dimeric species. The effect of the introduction of zinc(II) ions during the formation of the copper(II) chelates has been assessed in each case.