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

(PPh 4 ) 2 [TiCl 3 (NSiMe 3 )] 2 · CH 3 CN has been prepared from [TiCl 2 NSiMe 3 )] ∞ with PPh 4 Cl 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 PPh 4 + ions and centrosymmetric dimeric anions [TiCl 3 (NSiMe 3 )] 2 2- , in which pentacoordinate titanium atoms are associated via the nitrogen atoms of the silylimido groups. (PPh 4 ) 2 [TiCl 4 (OSPCl 2 )] 2 has been prepared by the reaction of PPh [OSPCl 2 ] with titanium tetrachloride in CH 2 C1 2 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 PPh 4 + ions and centrosymmetric dimeric anions [TiCl 4 (OSPCl 2 )] 2 2- , in which hexacoordinate titanium atoms are associated via two chlorine atoms. The OSPCl 2 - group is coordinated via the oxygen atom.