Syntheses and structures of Group 12 metal thioacetate anions, [M(SC{O}Me)nCl4−n]2− (n=3 and 4) and [Cd2Cl2(SC{O}Me)4]2−

We have utilized the possibility of altering the ratio of reactants to result in tetrahedral anions, [M(SC{O}Me)nCl4−n]2− (n=3, 4) and [Cd2Cl2(SC{O}Me)4]2−. Complexes of the formula [Ph4P]2[M(SC{O}Me)4] (M=Zn(II) (1), Cd(II) (2) or Hg(II) (3)) were synthesized by the reaction of thioacetate ligand with the metal salts and Ph4PCl in 4:1:2 molar ratio in suitable solvents. The geometry of Zn(II) in 1 is nearly tetrahedral and the distortion in tetrahedron increases in the order of 1<2<3 as observed from the SMS angles in the crystal structures. The tendency of monoanionic complexes [Ph4P][M(SC{O}Me)3] to react with 1 mole equivalent of Ph4PCl resulted in complexes of the type [Ph4P]2[M(SC{O}Me)3Cl] (M=Cd(II) (4) or Hg(II) (5)). In the structures of 4 and 5, three sulfur atoms and one chloride atom occupy the corners of the tetrahedron around the metal centers. However, in a 4:2:2 or 2:1:2 molar reaction of Me{O}CS− with CdCl2 and Ph4PCl in aqueous medium resulted in a chloro bridged dimer, [Ph4P]2[Cd2(μ-Cl)2(SC{O}Me)4] (6) as determined by X-ray crystallography.