“Constrained Geometry” Dialkyl Catalysts. Efficient Syntheses, C−H Bond Activation Chemistry, Monomer−Dimer Equilibration, and α-Olefin Polymerization Catalysis

Abstract

This contribution reports an efficient synthesis of the “constrained geometry” group 4 dibenzyl complexes Me2Si(η5-Me4C5)(tBuN)MR2 (CGCMR2, where R = CH2Ph; M = Ti (1), Zr (2)), as well as the substantially different reaction patterns in the cocatalytic activation of the R = CH2Ph and Me complexes with B(C6F5)3, PBB (tris(2,2‘,2‘‘-perfluorobiphenyl)borane), and Ph3C+B(C6F5)4-. The resulting cationic complexes are highly but not equivalently active for α-olefin polymerization and copolymerization catalysis. The reaction of the neutral free ligand CGCH2 with Ti(CH2Ph)4 in aromatic or saturated hydrocarbon solvents at 60 °C cleanly affords 1 in 90% yield, while the corresponding reaction with Zr(CH2Ph)4 produces 2 in lower yield. When activated with Ph3C+B(C6F5)4- at low temperatures, 2 generates cationic CGCZrCH2Ph+ B(C6F5)4- (4). However, unlike the corresponding metallocene dibenzyl, the cationic derivative of which (Cp2ZrCH2Ph+B(C6F5)4- (3)) can be isolated in quantitative yield, the reaction of 1 with B...