The chemistry of methyltitanium trichloride. Synthesis, properties, infrared spectra, and variable temperature nuclear magnetic resonance spectra of adducts of methyltitanium trichloride with symmetrical bidentate ligands

Abstract

A series of complexes of methyltitanium trichloride, with the general formula TiCl3Me,B has been prepared with the bidentate ligands (B) 1,2-dimethoxyethane, NNN′N′-tetramethylethylenediamine, 2,5-dithiahexane, 1,2-bisdiphenylphosphinoethane, NNN′N′-tetramethyl-o-phenylenediamine and NN-dimethyl-o-anisidine. The adducts are very air- and moisture-sensitive solids, which on storage in vacuo at ambient temperature, decompose with loss of the titanium methyl groups at rates which vary considerably with the nature of the ligand. The thermal decomposition and oxidation of these complexes have been investigated in an attempt to elucidate the factors affecting the reactivity of the titanium–carbon bond. The latter reaction has been found to yield the corresponding adducts of methoxytitanium trichloride, TiCl3MeO,B. Variable temperature n.m.r. studies of the methyltitanium trichloride complexes suggest that these prefer to adopt the meridional configuration.