Structural analysis of phenyl-germanium, -tin, and -lead dithiocarboxylates [(RCSS)(x)MPh4-x, M = Ge, Sn, Pb; x=1-3]: affinity between thiocarbonyl sulfur and Group 14 elements

A series of RCSSGePh3, (RCSS)(2)GePh2, (RCSS)(3)SnPh2 and (RCSS)(2)PbPh2 we re synthesized, and the structures of some p-tolyl derivatives [RCSSMPh3 (R = 4-CH3C6H4, M = Ge: 1d, Sn: 3d, Pb: 6d) and (4-CH3C6H4CSS)(2)SnPh2 (4d)] and a o-tolyl derivative [(2-CH3C6H4CSS)(3)SnPh: (5c)] were analyzed by X-r ay. The results indicate intramolecular non-bonded interactions between the thiocarbonyl sulfur and the central Group 14 element metals. The mono dith iocarboxylates (Id, 3d, and 6d) exhibit a distorted tetrahedral structure a round the central Group 14 elements. Diphenyltin bis(dithiocarboxylate) (4d ) is shown to take a distorted octahedron or skewed trapezoidal bipyramid, where the two dithiocarboxylate groups are hound to the Sn atom as an aniso bidentate ligand, and the tin tris(dithiocarboxylate) (5c) exhibits a seven -coordinated pentagonal bipyramid. The distance between the thiocarbonyl su lfur and the Sn atom in 4-CH3C6H4CSSMPh3 (M = Ge, Sn, Pb) is shorter than t hose in the corresponding germanium and lead derivatives. Based on these di stances, the affinity of Group 14 elements for sulfur atoms is deduced to d ecrease in the order Sn > Pb greater than or equal to Ge > Si > C. (C) 2000 Elsevier Science S.A. All rights reserved.