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

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 {[((t)Buo)(3)SiS]Zn-2(H2O)(n)}(m), and {[((t)BuO)(3)SiS](2) Zn(NH3)}(2) have been obtained. In acetonitrile as solvent I((t)BuO)(3)SiS](2) Zn(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 [((t)BuO)(3)SiS](2)ZnL(2) (L = py, 1-meimid or L(2) = bipy, phen). Some reactions leading to cadmium complexes were also performed. The crystal structures of two compounds were determined. Orthorhombic crystals of [((t)BuO)(3)SiS](2) Zn(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 [((t)BuO)(3)SiS]Zn-2(bipy) there is a ZnN2S2 core with distorted tetrahedral geometry.