Synthesis and structural characterisation of some highly hindered N-functionalised organoamido complexes of titanium(IV) and zirconium(IV)

Treatment of the group 4 halides TiCl4 and ZrCl4 with various stoichiometries of [(6-Me-TMS-Apy)Li(Et2O)] (6-Me-TMS-ApyH=2-(trimethylsilylamino)-6-methylpyridine) has been studied yielding [(6-Me-TMS-Apy)TiCl3]2 (1), [(6-Me-TMS-Apy)3TiCl] (2) or [(6-Me-TMS-Apy)3ZrCl] (3). The structures of compounds (1), (2) and (3) were characterised by spectroscopic and X-ray crystallographic methods. The X-ray structure of (1) is a centrosymmetric dimer through bridging chlorides. Compounds (2) and (3) are isostructural mononuclear complexes with seven-coordinate metal centres.