Reactivity of Early-Transition-Metal Fulvene Complexes. Transformation of a 2,3,4,5-Tetramethylfulvene Ligand into a Bidentate Dialkoxide with Four Asymmetric Carbon Atoms. Molecular Structure of Ti[(OCHPh)2C5Me4(CH2)]Cl2

摘要

Cp*FvTiCl (1; Cp* = η5-C5H5, Fv = η6-C5Me4CH2) reacts with benzaldehyde, yielding Cp*Ti[(OCHPh)2C5Me4(CH2)]Cl (2) as the result of insertion in two Ti-C bonds at the 2- and 4-positions of the fulvene ligand in 1. Complex 2 reacts with HCl to give Cp*TiCl3 (3) and the corresponding dialcohol and with TiCl4 to give 3 and Ti[(OCHPh)2C5Me4(CH2)]Cl2 (5). X-ray diffraction analysis of 5 shows it to be a dialkoxide-dichloride monomeric titanium complex with a tetrahedral arrangement of the ligands around the metal center. Crystal data for C24H26Cl2O2Ti: monoclinic, P21/n, a = 10.602 (5) Å, b = 14.157 (4) Å, c = 15.274 (5) Å, β = 103.76 (3)°, V = 2227 (1) Å3, Z = 4, R = 0.037.