Dinuclear titanium complexes with methylphenylsilylene bridge between cyclopentadienyl rings. Synthesis, characterization and reactivity towards ethylene

作者：Horacek Michal; Gyepes Robert; Merna Jan; Kubista Jiri; Mach Karel; Pinkas Jiri^*

来源：Journal of Organometallic Chemistry, 2010, 695(9): 1425-1433.

DOI：10.1016/j.jorganchem.2010.01.037

• Ansa-titanocene
• Cyclopentadienyl
• Dinuclear complexes
• Ethylene polymerization
• Crystal structure

The new ansa-titanocene dichloride [{(SiMePh)(eta(5)-C(5)H(4))(2)}TiCl(2)] (1) was prepared by one pot reaction, whereas synthesis of its methylated analogue [{(SiMePh)(eta(5)-C(5)Me(4))(2)} TiCl(2)] (3) was performed in two steps with isolation of corresponding silane intermediate SiMePh(HC(5)Me(4))(2) (2). The reaction of 1 and 3 with TiCl(4) afforded the dinuclear complexes [(SiMePh){(eta(5)-C(5)R(4))TiCl(3)}(2)] (R= H (4) and R = Me (5)). The catalysts formed from 4 and 5 after their activation with excess MAO exhibited a modest activity in ethylene polymerization. The polymer products consisted of high molar mass linear polyethylenes with a broad molar mass distribution. The presence of three paramagnetic titanium species in the mixture 4/MAO was revealed by EPR spectroscopy. All new prepared compounds 1-5 were characterized by multinuclear NMR, EI-MS, IR, and solid-state structures of 1, 3 and 5 were determined by X-ray single crystal diffraction.

• 出版日期2010-5-1