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The titanium β-diketiminato complexes (L1)TiCl2 (1), (L1)TiCl(N2,6-iPr2C6H3) (2), and (L2)2TiCl (3) [L1=(2,6-iPr2C6H3)NC(Me)CHC(Me)N(2,6-iPr2C6H3), L2=iPrNC(Me)CHC(Me)NiPr] have been prepared by the reaction of the lithium salt of the ligand, L, with titanium trichloride. Complex 2 was isolated from supernatant solutions of 1 containing excess of the (L1)Li salt. The monochloride complex [(L2)TiCl(NiPr)]2 (4) was prepared by reduction of (L2)2TiCl2 with the excess of Na/K alloy. Fluorination of the monochloride complex 3 with Me3SnF affords polymeric [(L2)TiF2]n (5). Oxidation of 5 gives the tetrameric complex, (L2)4Ti4F6O2·2toluene (6). Compounds 1–6 were characterized by single crystal X-ray structural analyses, elemental analyses, NMR and mass spectra. The bulky ligand (L1) stabilizes the Ti(III) complex 1 with an unusual distorted square-planar pyramidal geometry around the titanium atom, by sigma bonding to the metal. The less bulky ligand (L2) in complexes 3, 4 and 6 has mixed σ and π coordination to the titanium center. Investigation of the C&z.sbnd;C, N&z.sbnd;C distances in the NCCCN unit of the coordinated β-diketiminato ligands (L1) and (L2) demonstrated the localization of the double bonds in the ligand in complexes 1–3 and 6. The stability of the complexes in solution was studied by means of NMR spectroscopy. Complexes 2 and 4 are stable in solution, the polymeric and the tetrameric nature of complexes 5 and 6 is not evident in C6D6 solution. The (L2)2TiCl stoichiometry of the complex is unstable. [Copyright &y& Elsevier]