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Dinuclear titanium complexes with methylphenylsilylene bridge between cyclopentadienyl rings. Synthesis, characterization and reactivity towards ethylene |
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| Authors: | Michal Horá ?ek,Jan Merna,Karel Mach |
| Affiliation: | a J. Heyrovský Institute of Physical Chemistry of ASCR, v.v.i. Dolejškova 2155/3, 182 23 Prague 8, Czech Republic b Department of Inorganic Chemistry, Charles University, Hlavova 2030, 128 40 Prague 2, Czech Republic c Department of Polymers, Institute of Chemical Technology, Prague, Technická 5, 166 28 Prague 6, Czech Republic |
| Abstract: | The new ansa-titanocene dichloride [{(SiMePh)(η5-C5H4)2}TiCl2] (1) was prepared by one pot reaction, whereas synthesis of its methylated analogue [{(SiMePh)(η5-C5Me4)2}TiCl2] (3) was performed in two steps with isolation of corresponding silane intermediate SiMePh(HC5Me4)2 (2). The reaction of 1 and 3 with TiCl4 afforded the dinuclear complexes [(SiMePh){(η5-C5R4)TiCl3}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. |
| Keywords: | Ansa-titanocene Cyclopentadienyl Dinuclear complexes Ethylene polymerization Crystal structure |
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