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<TiBr4 and MeC(CH2SMe)3<MeC(CH2SeMe)3 and attempts to isolate TiI4 analogues were unsuccessful. The reactions of [MCl4(Me2S)2] (M=Zr or Hf) with (L3) in anhydrous CH2Cl2 produces white or cream 7-coordinate [MCl4(L3)], which are insoluble in chlorocarbon solvents. The reactions of TiX4 (X=Cl, Br or I) with the trithia-macrocycles [9]aneS3 and [10]aneS3 produced [TiX3([n]aneS3)]X, whilst reaction of TiCl4, SbCl5 and [9]aneS3 in anhydrous CH2Cl2 gave [TiCl3([9]aneS3)]SbCl6. Spectroscopic studies suggest these macrocyclic compounds contain 6-coordinate cations, [TiX3([n]aneS3)]+ (n=9 or 10) but with Zr and Hf the complexes [MCl4([n]aneS3)] are 7-coordinate and neutral.