Trends in Structure and Ethylene Polymerization Reactivity of Transition-Metal Permethylindenyl-phenoxy (PHENI*)...

A family of ansa-permethylindenyl-phenoxy (PHENI*) transition-metal chloride complexes has been synthesized and characterized (1-7; {(η⁵-C₉Me₆)Me(R″)Si(2-R-4-R'-C₆H₂O)}MCl₂; R,R' = Me, Bu, Cumyl (CMe₂Ph); R″ = Me, Pr, Ph; M = Ti, Zr, Hf). The ancillary chloride ligands could readily be exchanged with halides, alkyls, alkoxides, aryloxides, or amides to form PHENI* complexes [L]TiX₂ (8-17; X = Br, I, Me, CH₂SiMe₃, CH₂Ph, NMe₂, OEt, ODipp). The solid-state crystal structures of these PHENI* complexes indicate that one of two conformations may be preferred, parametrized by a characteristic torsion angle (TA'), in which the η⁵ system is either disposed away from the metal center or toward it. Compared to indenyl PHENICS complexes, the permethylindenyl (I*) ligand appears to favor a conformation in which the metal center is more accessible. When heterogenized on solid polymethylaluminoxane (sMAO), titanium PHENI* complexes exhibit exceptional catalytic activity toward the polymerization of ethylene. Substantially greater activities are reported than for comparable PHENICS catalysts, along with the formation of ultrahigh-molecular-weight polyethylenes (UHMWPE). Catalyst-cocatalyst ion pairing effects are observed in cationization experiments and found to be significant in homogeneous catalytic regimes; these effects are also related to the influence of the ancillary ligand leaving groups in slurry-phase polymerizations. Catalytic efficiency and polyethylene molecular weight are found to increase with pressure, and PHENI* catalysts can be categorized as being among the most active for the controlled synthesis of UHMWPE.