Titanium, zirconium and hafnium halide complexes of trithioether and triselenoether ligands

The reaction of TiX4(X=Cl or Br) with the tripodal ligands MeC(CH2SMe)3 or MeC(CH2SeMe)3, (L3) in anhydrous n-hexane or CH2Cl2 produced the extremely moisture sensitive complexes [TiX4(L3)]. These were characterised by microanalysis, IR, UV–Vis and variable temperature 1H,13C{1H} and 77Se NMR spectroscopy. The NMR studies showed that in solution in CH2Cl2 the complexes contain L3 bound as bidentates, and that pyramidal inversion and exchange between the free and coordinated chalcogen donors is rapid at room temperature. Ligand dissociation/exchange increases TiCl4