Abstract
Half titanocene complexes bearing pyridinethiolate ligands, Cp*TiCl2(SPy) (1, Cp*=η5-pentamethylcyclopentadienyl, SPy=2-pyridinethiolate) and Cp*TiCl(3-R-SPy)2·H(3-R-SPy) (3-R-SPy=3-R-2-pyridinethiolate: R=H (2a), Me3Si (2b)), were synthesized by the reaction of Cp*TiCl3 and one or two equivalents of K(3-R-SPy). The structure of 2a was revealed by X-ray crystallography. The 1-MMAO (MMAO=modified methylaluminoxane) system showed moderate activity for ethylene polymerization to give linear polyethylene with high molecular weight and relatively narrow molecular weight distribution. The 2a- and 2b-MMAO systems showed lower activity than that of 1-MMAO. The 1-MMAO system also polymerized styrene to produce highly syndiotactic polystyrene, while the 2a- and 2b-MMAO systems were almost inactive for styrene polymerization.
