| Abstract: | Reactivity of Tris(dialkylthiophosphinyl)phosphines – Crystal Structure of [Ag{O[P(S)Me2]2}2][AsF6] In contrast to tris(dialkylphosphoryl)phosphines the reaction of tris(dimethylthiophosphinyl)phosphine with transition metal hexafluoroarsenates of the type [M(SO2)m [AsF6]n (M = Ag, m = 0, n = 1; M = Fe, Cd, m = n = 2) forms no molecular 2 : 1-complexes but polymeric products. The silver polymer is transformed into [Ag{O[P(S)Me2]2}2][AsF6], which is also formed by the reaction of Ag[AsF6] with O[P(S)Me2]2. It crystallizes in the space group P1 with a = 862.5(2), b = 1 241.4(2), c = 1 254.0(3)pm, α = 80.34(1), β = 101.99(6), γ= 73.75(1)° (at 20°C) and Z = 2. The central silver atom is surrounded by four sulphur atoms in a slighly distorted tetrahedron. The average (Ag? S) and (P? S) bond lengthes are 259.4(2) pm and 194.9(2)pm, respectively. |
