Preparation and X-ray crystal structure of (Ph 3P) 2PtS 2N 2·C 7H 8: a reinvestigation of the reaction of S 4N 4H 4 with (Ph 3P) 4Pt

Abstract

The reaction of S 4N 4H 4 with (Ph 3P) 4Pt in toluene produces the yellow complex (Ph 3P) 2PtS 2N 2·C 7H 8 shown by X-ray crystallography to contain a five- membered metallathiazene ring with PtN = 2.093(9) Å, PtS = 2.294(6) Å and two short [1.499(16) and 1.548(12) Å and one long [1.702(15) Å] SN bonds. The crystals are triclinic with space group P 1 ; a = 11.328(2); b = 12.366(2); c = 16.822(3) Å; α = 94.12(1); β = 108.57(1); γ = 112.93(1)°; V = 2004.8(2) Å 3; Z = 2. The final R and R w values were 0.047 and 0.058, respectively. The same complex is obtained from the reactions of (Ph 3P) 4Pt with S 4N 4 or (Ph 3P) 2PtC 2H 4 with S(NSO) 2. The reaction of NiCl 2 with a mixture of S 4N 4H 4 and the Wittig reagent, Ph 3PCH 2, produces Ni(S 2N 2H) 2. The mechanisms of the reactions of S 4N 4H 4 and S 4N 4 with electron-rich metal centres are discussed briefly.