Metallocene-Catalyzed Propene Polymerization: From Microstructure to Kinetics. 1. C2-Symmetric ansa-Metallocenes and the "Trigger" Hypothesis

A microstructural method for the determination of the reaction order with respect to the monomer in coordinated 1-alkene polymerizations is proposed. The method is applicable whenever enantioselective monomer polyinsertion competes with an intramolecular process introducing stereodefects of known and recognizable nature in the growing polymer chains at a rate independent of monomer concentration, [M] (e.g., chain or site epimerization for C-2-symmetric and C-s-symmetric ansa-metallocene catalysts, respectively). Indeed, in such cases, the stereoregularity of the polymer obtained at a given temperature results from the balance between the rates of the two competing processes, and is obviously a function of [M] because so is the rate of polyinsertion, <upsilon(p)>. Therefore, from the way polymer stereoregularity changes with [M], the corresponding change of <upsilon(p)> can be inferred. Compared with the conventional macroscopic approach based on measurements of monomer consumption, the microstructural route is more reproducible, and allows one to discriminate between "authentic" and apparent higher-order polyinsertion rate laws. In this paper, in particular, we show that the "trigger" hypothesis invoked to explain the observed pseudo-second-order kinetics of propene polymerization promoted by C-2-symmetric ansa-metallocene catalysts is inconsistent with the experimental results and that an alternative explanation assuming first-order kinetics at catalytic species which interconvert between a propagating and a "resting" state is more plausible.