Substituent Effects of Phenyl Group on Silylene Bridge in Stereospecific Polymerization of Propylene with C1-Symmetric Ansa-Silylene(fluorenyl)(amido) Dimethyl Titanium Complexes

A C-1-symmetric (methylphenyl)silylene-bridged (fluorenyl)(naphthylamido) titanium complex (1) and (diphenyl)silylene-bridged (fluorenyl)(naphthylamido) titanium complex (2) were synthesized and characterized by H-1 NMR, element analysis, and X-ray crystal analysis. The coordination mode of the fluorenyl ligand to the titanium metal is an eta(3) manner in each complex. These complexes were applied for propylene polymerization using dried modified methyaluminoxane (dMMAO) as a cocatalyst under different propylene pressures in a semi batch-type method. The catalytic activity was strongly dependent on the structure of the complex and the propylene pressure, where complex 1 exhibited the highest activity (600 kg mol(-1).h(-1)) under a propylene pressure of 8.0 atm to produce high molecular weight polypropylene. The polypropylenes obtained were syndiotactic-rich with an rr value of 0.50, indicating that the silylene bridge was not efficient for the isospecificity of a constrained geometry catalyst (CGC). The mechanical properties of the resulting polymers depended on their microstructure.