Organomercury complexes bearing (thioxothiazolidin-5-yl)methyl moiety by intramolecular heteromercuration reaction of diallyldithiocarbamate

Abstract

Reaction of diallyldithiocarbamate and mercury chloride in different mole ratios afforded two different organomercury complexes: ((3-allyl-2-thioxothiazolidin-5-yl)methyl)mercury(II) chloride and N,N-diallyl-dithiocarbamat(3-allyl-2-thioxothiazolidin-5-yl)methyl)mercury(II) represented as complex 1 and 2 respectively. The complexes were characterized by microanalysis, spectroscopic (IR, 1H and 13C NMR) techniques and their structures were elucidated by X-ray crystallography. Formation of both complexes occurred by intramolecular solvomercuration reactions via the allylic double bond. This reaction pathway was favoured by the properties of the reactants used: mercury chloride and an alkenamine derivative. The dithiocarbamate moeiety acted as a highly nucleophilic neighbouring group, and induced heterocyclization process by anchimeric assistance leading to formation of thiazol, a five-membered ring in both complexes. The structure of complex 1 presents a mercury compound in which the positive charge of the Hg2+ atom is balanced by dithiocarbamato and chloride anions acting as monodentate ligands, while in complex 2 the Hg atom is coordinated to three dithiocarbamate ligands and a ring closure occurred with one of the S atoms forming a thiazole ring.