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A series of ansa -silylene(fluorenyl)(amido) titanium complexes ( 1a ⁻ 1c , 2a , and 2b ) bearing various substituents on the amido and fluorenyl ligands are synthesized and characterized by elemental analysis, ¹H NMR, and single crystal X-ray analysis. The coordination mode of the fluorenyl ligand to the titanium metal is η³ manner in each complex. The propylene polymerization is conducted with these complexes at 0 and 25 °C in a semi batch-type method, respectively. The catalytic activity of 1a ⁻ 1c bearing cumyl-amido ligand is much higher than that of 2a and 2b bearing naphthyl group in amido ligand. High molecular weight polypropylenes are obtained with narrow molecular weight distribution, suggesting a living nature of these catalytic systems at 0 °C. The polymers produced are statistically atactic, regardless of the structure of the complex and the polymerization temperature.

Living Polymerization of Propylene with ansa-Dimethylsilylene(fluorenyl)(cumylamido) Titanium Complexes