Die Kristallstrukturen von (PPh4)2[TiCl3(NSiMe3)]2 • CH3CN und (PPh4)2[TiCl4(OSPCl2)]2 / The Crystal Structures of (PPh4)2[TiCl3(NSiMe3)]2 · CH3CN and (PPh4)2[TiCl4(OSPCl2)]2

Abstract

(PPh4)2[TiCl3(NSiMe3)]2 · CH3CN has been prepared from [TiCl2NSiMe3)]∞ with PPh4Cl in acetonitrile solution as yellow crystals. The compound crystallizes in the triclinic space group P T with one formula unit per unit cell, 3447 observed unique reflections, R = 0.053. Lattice dimensions at 200 K: a = 1030(1), b = 1253(1), c = 1374(1) pm, α = 77.46(8)°, β = 73.93(8)°, γ = 69.99(9)°. The structure consists of PPh4 + ions and centrosymmetric dimeric anions [TiCl3(NSiMe3)]2 2-, in which pentacoordinate titanium atoms are associated via the nitrogen atoms of the silylimido groups. (PPh4)2[TiCl4(OSPCl2)]2 has been prepared by the reaction of PPh [OSPCl2] with titanium tetrachloride in CH2C12 solution as orange crystals. (Space group P1̄, Ζ = 1, 3242 observed unique reflections, R = 0.033). Lattice dimensions at 193 K: a = 1114.8(2), b = 1190.6(2), c = 1218.7(2) pm, α = 72.18(1)°, β = 85.45(1)°, γ = 69.19(1)°. The structure consists of PPh4 + ions and centrosymmetric dimeric anions [TiCl4(OSPCl2)]2 2-, in which hexacoordinate titanium atoms are associated via two chlorine atoms. The OSPCl2- group is coordinated via the oxygen atom.