Silanolato-Komplexe von Titan und Zirconium. Die Kristallstrukturen von Cp2TiCl(OSiPh3) und Cp2ZrCl(OSiPh3)

Silanolato Complexes of Titanium and Zirconium. The Crystal Structures of Cp₂TiCl(OSiPh₃) and Cp₂ZrCl(OSiPh₃) The title compounds have been prepared by the reaction of Cp₂MCl₂ (M = Ti, Zr) with triphenylsilanole in diethylether in the presence of piperidine. They form only sparingly moisture sensitive orange (Ti) or colourless (Zr) crystal needles, which were characterized by X-ray crystallography. Cp₂TiCl(OSiPh₃): Space group P2₁/n, Z = 4, structure solution with 3961 observed unique reflections, R = 0.057. Lattice dimensions at 20°C: a = 1029.6, b = 1719.3, c = 1388.9 pm, β = 100.69°. The compound forms monomeric molecules with bond lengths TiO of 184.2 pm, SiO of 161.5 pm, and a TiOSi bonding angle of 164.5°. Cp₂ZrCl(OSiPh₃): Space group P3 , Z = 18, structure solution with 2799 observed unique reflections, R = 0.047. Lattice dimensions at ?20°C: a = b = 3518, c = 1058.3 pm. The structure consists of three symmetry-independent monomeric molecules, which differ only slightly. The bond lengths are (in average): ZrO 196.4 pm, SiO 162.1 pm, the ZrOSi bond angle is 173.7°.