Zinc complexes with pyrimidine-2-thionato ligands with the general formula [Zn(RpymS) 2 ] can be easily obtained by electrochemical oxidation of a zinc anode in a cell containing an acetonitrile solution of the appropriate thione (RpymSH, R=4,6-Me 2 ,5-Et; 4-CF 3 and 4,6-CF 3 ,Me). When 2,2′-bipyridine (bipy) or 1,10-phenanthroline (phen) were added to the cell, the corresponding adducts [Zn(RpymS) 2 L] were also obtained (L=bipy, phen). All of the compounds have been characterized by microanalysis, mass spectrometry, IR spectroscopy and, for compounds that were sufficiently soluble, by 1 H and 13 C NMR spectroscopy. The compounds [Zn(4,6-Me 2 ,5-EtpymS) 2 (MeOH)] (4), [Zn(4-CF 3 pymS) 2 (phen)] (7) and [Zn(4,6-CF 3 ,MepymS) 2 (bipy)] (9) were also characterized by X-ray diffraction. The structures of all of these complexes consist of discrete molecules. In complex 4, the pyrimidine-2-thionato acts as an S,N bidentate chelating ligand. The coordination number for Zn is five and the fifth position is occupied by an oxygen atom from a methanol molecule. In 7 and 9, the coordination number for the metal centre is four. In these cases the thionato ligands show a monodentate behaviour, using the exocyclic sulfur to bind the zinc atom.