Synthesis and structure of platinum complexes [Ph4P]+[PtCl3(DMSO)]− and [Ph4P]+[PtCl5(DMSO)]

The reaction of tetraphenylphosphonium chloride with an equimolar amount of potassium tetrachloroplatinate or hexachloroplatinic acid in dimethyl sulfoxide gave the complexes [Ph 4 P] + [PtCl 3 (DMSO)] − ( I ) and [Ph 4 P] + [PtCl 5 (DMSO)] − ( II ), respectively. The phosphorus atoms in the cations have tetrahedral environment, the CPC angles and P-C distances 105.63(13)°–112.13(14)°, 1.795(3)–1.797(3) Å I ) and 105.7(3)°–112.9(3)°, 1.783(7)–1.791(6) Å II ). The platinum coordination polyhedra in the anions [PtCl 3 (DMSO)] − and [PtCl 5 (DMSO)] − are distorted square (Pt-S, 2.1937(8); Pt-Cl, 2.2894(10)–2.3024(10) Å; trans -angles: SPtCl, 177.38(4)°; ClPtCl, 175.40(4)°) and octahedron (Pt-S 2.291(2) Å; Pt-Cl, 2.312(2)–2.334(2) Å, trans -angles: SPtCl, 178.28(9)°; ClPtCl, 178.80(9)° and 178.88(8)°).