An example of an "inverted" tetrahedral geometry at sulfur. The synthesis and crystal and molecular structure of [HPtOs3(CO)8(μ4-S)(μ 3-S)(PPh2C6H4)]2

Abstract

The decarbonylation of the sulfido-bridged cluster PtOs3(CO)10(PPh3)(M3-S)2, 1, by trimethylamine oxide leads to formation of the dimer [HPtOs3(CO)8(μ4-S)(μ 3-S)(PPh2C6H4]2, 2. The molecular structure of 2 was determined by single-crystal X-ray diffraction analysis: space group P21/n, a = 14.308 (2) Å, b = 21.753 (5) Å, c = 21.760 (4) Å, β = 96.20 (1)°, Z = 4, ρcalcd = 2.83 g/cm3. The structure was solved by a combination of direct methods and difference Fourier techniques and was refined with 4874 reflections to the final residuals of RF = 0.053 and RwF = 0.063. Compound 2 consists of two trigonal-prismatic PtOs3S2 clusters linked on an edge by quadruply bridging sulfido ligands that serve as six-electron donors and exhibit inverted tetrahedral geometries. © 1984 American Chemical Society.