Synthesis and styrene polymerization properties of dinuclear half-titanocene complexes with xylene linkage

The new dinuclear half-sandwich complexes of titanium with xylene bridge, [Ti(η5-cyclopentadienyl)Cl2L]2[CH2–C6H4–CH2] (L = Cl (3), L = O-2,6-iPr2C6H3 (4), L = N(SiMe3)(2,6-Me2C6H3) (5)), have been synthesized. The complexes 4 and 5 have been prepared by the reaction of the complex 3 with the corresponding lithium salts of aryloxy and anilide. Structure of these complexes has been characterized by 1H and 13C NMR. The change of substituent from chloride, 3, to anilide, 5, at titanium resulted in chemical shift change of cyclopentadienyl protons from 6.92 and 6.79 to 6.13 and 5.95 ppm probably due to the positive electron density delivery from the anilide group. It was found that all three half-titanocenes were effective catalyst for the generation of SPS (syndiotactic polystyrene). Xylene bridged dinuclear catalyst (4) with aryloxy substituent exhibited very high activity (458 kg of SPS/(mol of [Ti])h), at 40 °C, whereas the analogous hexamethylene bridged dinuclear half-titanocene catalyst (7) showed a lower activity (80.7 kg of SPS/(mol of [Ti])h) under the same conditions. While the catalyst 3 was the most active catalyst among three complexes less than 40 °C the catalyst 5 exhibited the highest activity at 70 °C. Xylene linkage was suggested to be too stiff to permit any kind of intramolecular interaction between two active centers. Lack of steric disturbance due to the rigidity of the xylene bridge might give rise to the similar properties of dinuclear metallocene to the corresponding mononuclear metallocene to result in not only the facile coordination of monomer at the active center to lead high activity but also the easier β-H elimination comparing to the dinuclear catalysts with the flexible bridge to result in the formation of lower molecular weight polymer.

Graphical abstractThe new dinuclear half-sandwich complexes of titanium with xylene bridge, [Ti(η5-cyclopentadienyl)Cl2L]2[CH2–C6H4–CH2] (L = Cl (3), L = O-2,6-iPr2C6H3 (4), L = N(SiMe3)(2,6-Me2C6H3) (5)), have been synthesized by the reaction of the complex 3 with the corresponding lithium salts of aryloxy and anilide. Structure of these complexes has been characterized by 1H and 13C NMR. It was found that all three half-titanocenes were effective catalyst for the generation of SPS (syndiotactic polystyrene). Xylene bridged dinuclear catalyst (4) with aryloxy substituent exhibited very high activity (458 kg of SPS/(mol of [Ti])h), at 40 °C, whereas the analogous hexamethylene bridged dinuclear half-titanocene catalyst (7) showed a lower activity (80.7 kg of SPS/(mol of [Ti])h) under the same conditions.Figure optionsDownload full-size imageDownload as PowerPoint slide