Preparation of the hydrocarbon-soluble trifluoro complex LTiF3 with a β-diketiminato ligand

The β-diketiminato fluoride complex (LTiF3) (1) (L = HC(CMeN(2,6-iPr2C6H3))2, “NacNac”) has been obtained using two synthetic routes, interaction of TiF4 and NacNacK·2THF in toluene and interaction of LTiCl3 and 3 equiv. of Me3SnF in toluene. The trifluoro complex (LTiF3) (1) is soluble in the non-polar solvents toluene and hexane and moderately active in polymerization of ethylene; the activity is higher than that of LTiMe3 and comparable with that of the oxo-bridged complexes LTiCl(μ-O)2TiClL and LTiMe(μ-O)2TiMeL·toluene. Compound 1 was characterized by single crystal X-ray structural analysis, elemental analysis, NMR spectroscopy, and mass spectrometry. Complex 1 in the solid state is a centrosymmetric dimer containing two LTiF2 moieties connected by two bridging fluorines, whereas C6D6 and CD3CN solutions of 1 contain the monomeric complex at room temperature.