Chemistry of platinum sulphido-complexes. Part 4. Dimeric μ-alkyl-sulphido-complexes: Crystal and molecular structures of [Pt2(μ-S)-(μ-SMe)(PPh3)4]PF 6·MeOH and cis-[Pt2(μ-SMe)2(NO2)2(PPh 3)2]

Abstract

A study of the reactions of [Pt2(μ-S)2(PPh3)4] with halogenoalkanes has led to the isolation and and characterisation (1H, 13C, 31P, and 195Pt n.m.r.) of the complexes [Pt2(μ-S)(μ-SR)(PPh3)4]Y (R = Me or CH2Cl; Y = Cl, I, PF6, or BPh4). The molecular structure of [Pt2(μ-S) (μ-SMe) (PPh3)4]-PF6·MeOH has been determined by single-crystal X-ray techniques using diffractometer data. The compound crystallises in the monoclinic space group P21/c with four formula units in a cell of dimensions a = 22.835(7), b = 13.094(4), c = 24.357(9) Å, and β = 110.99(3)°. Least-squares refinement of the structure has led to the final R value of 0.056 using 3 551 observed intensities [I ≥ 3σ(I)]. The related methylsulphido-complex cis-[Pt2(μ-SMe)2(NO2)2(PPh 3)2] has been isolated from the reaction of [Pt(SMe)2(PPh3)2] and NO gas and characterised by single-crystal X-ray analysis. The compound crystallises in the triclinic space group P1 with cell dimensions a = 10.476(3), b = 12.781 (2), c = 16.814(4) Å, α = 111.27(2), β = 93.79(2), γ = 76.06(2)°, and Z = 2. Least-squares refinement led to a final R factor of 0.062 using 3 138 reflections having I ≥ 3σ(I).