The synthesis of titanium(IV) Schiff base complexes has been investigated using the tetradentate salen ligand and its derivatives [L = salenH₂ = N,N′-bis(salicylidene)ethylenediamine]. Complexes of the form [TiX₂(L)], [(thf)TiX₂(L)] and [TiX₄(LH₂)] have been observed with the nature of these products being dependent on the salen derivative, halide and reaction condition employed. The reaction of [(thf)₂TiF₄] with salenH₂ yields the complex [TiF₄(salenH₂)] 1 which does not eliminate HF to form [TiF₂(salen)] 2 even after toluene reflux. Compound 2 can be obtained in 90% yield using the silylated Schiff base salen(TMS)₂ (TMS = Me₃Si) and [(thf)₂TiF₄] in thf. Compound 2 has been characterised by single crystal X-ray diffraction. Refluxing an equimolar ratio of salenH₂ and TiCl₄ gave the previously prepared [TiCl₂(salen)] 3, while stirring the same reactants at room temperature afforded the seven-coordinate solvent adduct [(thf)TiCl₂(salen)] 4 in quantitative yield. TiBr₄ reacts similarly with salenH₂ or salen(TMS)₂ to give [TiBr₂(salen)] 5. The bromide analogue of 4 was identified from its characteristic FAB⁺ mass spectrum. Reaction of TiI₄ with salen(TMS)₂ or salenH₂ in thf or MeCN gave the µ-oxo bridged species [TiI(salen)]₂(µ-O) 6 in preference to the iodide analogue of [TiX₂(salen)]. Substituted Schiff bases (MeO)₂salenH₂, salphenH₂ and (MeO)₂salphenH₂ [salphenH₂ = N,N′-bis(salicylidene)-1,2-phenylenediamine] react with TiCl₄ (1∶1) to yield the corresponding dichloride complexes [TiCl₂(L)] [L = (MeO)₂salen 7, salphen 8, (MeO)₂salphen 9] via the elimination of HCl. In contrast, the α-methylated salen derivative dmsalenH₂ [N,N′-bis(α-methylsalicylidene)ethylenediamine] reacts in an analogous manner to the TiF₄–salen system affording [TiCl₄(dmsalenH₂)] 10.