LAUSR

1-Hexene polymerization using four zirconium-based amine bis(phenolate) catalysts, Zr[2-R-4-tBu-ONNO]Bn2 (where R = methyl (1), ethyl (2), isopropyl (3), and tert-butyl (4)), was examined to establish the effect of ligand sterics on kinetics and stereocontrol of olefin polymerization. For each catalyst, a rich data set was obtained including monomer consumption, molecular weight evolution, end-group analysis, and active site counts. A set of reaction specific rate constants was determined for catalysts 2–4. In addition to the standard elementary reaction steps of initiation, propagation, mis-insertion, and chain transfer, these catalysts undergo isomerization leading to dormancy. This isomerization is particularly prominent in bromobenzene and for less sterically hindered complexes. Across the series 2–4, ligand steric properties have a systematic effect on both insertion and chain transfer rate constants. This relationship was rationalized using the Sterimol steric parameters. The rates of propagation an...