Titanium and zirconium complexes bearing new tridentate [OSO] bisphenolato-based ligands: synthesis, characterization and catalytic properties for alkene polymerization.

A number of new sulfur-bridged tridentate [OSO] bisphenolato-based ligand precursors S(2-CH2-4-tBu-6-R-C6H2OH)2 [R = CMe3 (H2L1), CMe2Ph (H2L2), CMePh2 (H2L3), CPh3 (H2L4), and C(p-Tol)3 (H2L5)] were synthesized by reactions of Na2S·9H2O with 2 eq. of the corresponding 2-(bromomethyl)-4-(tert-butyl)-6-R-phenol. Their neutral titanium complexes [S(2-CH2-4-tBu-6-R-C6H2O)2]TiCl2 [R = CMe3 (1), CMe2Ph (2), CMePh2 (3), CPh3 (4), and C(p-Tol)3 (5)] were synthesized in high yields by direct HCl-elimination reactions of TiCl4 with the corresponding ligand precursors in toluene. Ionic titanium complexes [NHEt3][S(2-CH2-4-tBu-6-R-C6H2O)2TiCl3] [R = CMe3 (6), CMePh2 (7)] and [NH2Et2][S(2-CH2-4-tBu-6-R-C6H2O)2TiCl3] [R = CMe3 (8) and CMePh2 (9)] were obtained in high yields from the reactions of TiCl4 with the corresponding ligand precursors in the presence of 2 eq. of triethylamine or diethylamine. Neutral zirconium complexes [S(2-CH2-4-tBu-6-R-C6H2O)2]ZrCl2(THF) [R = CMe2Ph (10·THF), and CMePh2 (11·THF)] were synthesized by reactions of ZrCl4 with 1 eq. of the dilithium salt of the corresponding ligand precursors Li2L in THF. The new titanium and zirconium complexes were characterized by 1H and 13C NMR, IR and elemental analyses. The molecular structures of complexes 4, 6 and 10·THF were determined by single-crystal X-ray diffraction analysis. The X-ray crystallography analysis reveals that titanium complex 4 has a five-coordinating environment surrounding the central metal atom, while the titanium complex 6 and the THF-solvated zirconium complex 10·THF possess a six-coordinating pseudo-octahedral environment around the central metal atom. Upon activation with MAO or AliBu3/Ph3CB(C6F5)4, all these titanium and zirconium complexes exhibit moderate to high catalytic activities for ethylene polymerization and ethylene/1-hexene copolymerization with moderate to high comonomer incorporation, and the ionic titanium complexes 6, 7, 8 and 9 show lower catalytic activity than their corresponding neutral complexes under similar conditions.