6533b872fe1ef96bd12d2c61

RESEARCH PRODUCT

Sulphides of the platinum group elements—12. Bis(tetraphenylphosphonium) pentakaidekakissulphido platinates(IV)

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Abstract Synthetic routes to tetraphenylphosphonium salts of [PtSx]2− are outlined, where x = 15 or 18. Generally, (PPh4)2[Pt(S5)3] is formed most readily. The compound [(C6H5)4P]2[PtS15], always solvated, has been obtained by synthesis in acetonitrile (sulphur, triethylamine, H2S and [PPh4]2[PtCl6]) and by metathesis (in DMF) from the known hydrated ammonium compound (NH4)2[Pt(S5)3]2H2O+2[Ph4P]Br→(Ph4P)2[Pt(S5)3]· DMF+2NH4Br, and from the dismutation (in acetone) 3PtS172−→PtS152−+2PtS182−. X-ray diffraction shows that crystals obtained from DMF and acetone are the solvated salts [Ph4P]2· [Pt(S5)3]· S, with solvent molecules (S) uncoordinated. In both, the three platinopentathian rings related by a three-fold axis of the anion have the chair conformation. Molecules of the solvent are located between the anion and cation.