The β-diketiminato fluoride complex (LTiF 3 ) (1) (L=HC(CMeN(2,6-iPr 2 C 6 H 3 )) 2 , “NacNac”) has been obtained using two synthetic routes, interaction of TiF 4 and NacNacK·2THF in toluene and interaction of LTiCl 3 and 3equiv. of Me 3 SnF in toluene. The trifluoro complex (LTiF 3 ) (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 LTiMe 3 and comparable with that of the oxo-bridged complexes LTiCl(μ-O) 2 TiClL and LTiMe(μ-O) 2 TiMeL·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 LTiF 2 moieties connected by two bridging fluorines, whereas C 6 D 6 and CD 3 CN solutions of 1 contain the monomeric complex at room temperature.