Zinc silanethiolates: Synthesis and properties. Crystal structures of bis(tri-tert-butoxysilanethiolato)(acetonitrile)zinc(II) and bis(tri-tert-butoxysilanethiolato)(bipyridine)zinc(II)

Abstract

Reactions of tri-tert-butoxysilanethiol with inorganic zinc compounds such as [Zn(H2O)4]2+, [Zn(NH3)4]2+, basic zinc carbonate, ZnCl2 or with metallic zinc in water, benzene, or in the absence of solvent are described. Heteroleptic zinc silanethiolates such as {[(tBuO)3SiS]2Zn(H2O)n}m, and {[(tBuO)3SiS]2Zn(NH3)}2 have been obtained. In acetonitrile as solvent [(tBuO)3SiS]2Zn(NCMe) is formed. All three of these new complexes reacted with the strong nitrogen donor species pyridine, 1-methylimidazole, 2,2′-bipyridine and 1,10-phenanthroline to give complexes of formula [(tBuO)3SiS]2ZnL2 (L = py, 1-meimid or L2 = bipy, phen). Some reactions leading to cadmium complexes were also performed. The crystal structures of two compounds were determined. Orthorhombic crystals of [(tBuO)3SiS]2Zn(NCMe) consist of molecules in which the zinc atom is bonded to two sulphur atoms, two oxygen atoms and one nitrogen atom in a distorted trigonal bipyramidal arrangement. In the triclinic crystals [(tBuO)3SiS]2Zn(bipy) there is a ZnN2S2 core with distorted tetrahedral geometry.