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

Abstract

We have utilized the possibility of altering the ratio of reactants to result in tetrahedral anions, [M(SC{O}Me) n Cl 4− n ] 2− ( n=3, 4) and [Cd 2Cl 2(SC{O}Me) 4] 2−. Complexes of the formula [Ph 4P] 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 Ph 4PCl 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 [Ph 4P][M(SC{O}Me) 3] to react with 1 mole equivalent of Ph 4PCl resulted in complexes of the type [Ph 4P] 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 CdCl 2 and Ph 4PCl in aqueous medium resulted in a chloro bridged dimer, [Ph 4P] 2[Cd 2(μ-Cl) 2(SC{O}Me) 4] ( 6) as determined by X-ray crystallography.