Chemistry of platinum sulphido-complexes. Part 4. Dimeric µ-alkyl-sulphido-complexes: crystal and molecular structures of [Pt2(µ-S)-(µ-SMe)(PPh3)4]PF6·MeOH and cis-[Pt2(µ-SMe)2(NO2)2(PPh3)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(PPh₃)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 P 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).