Revisiting Stereoselective Propene Polymerization Mechanisms: Insights through the Activation Strain Model

: The stereoelectronic factors responsible for stereoselectivity in propene polymerization with several metallocene and post-metallocene transition metal catalysts have been revisited using a combined approach of DFT calculations, the Activation Strain Model, Natural Energy Decomposition Analysis and a molecular descriptor (%VBur). There are in most cases two different paths leading to the formation of stereoerrors (SE), and the classical model does not suffice to fully understand stereoregulation. Improving stereoselectivity requires raising the energies of both SE insertion transition states. Our analyses show that the degrees of deformation of the active site (catalyst+chain) and the prochiral monomer differ for these two paths, and between different catalyst classes. Based on such analyses we discuss: a) the subtle differences in SE formation between stereoselective catalysts with different ligand frameworks; b) the reason for exceptional stereoselectivity reported for a special ansa-metallocene catalyst; c) the (double) stereocontrol origin for isoselective catalysts; d) the electronic contribution for isoselective catalysts generating SE by a modification of the ligand wrapping mode during the polymerization. Although this study will not immediately suggest new catalyst structures, we believe that understanding stereoregulation in great detail will increase our chances of success.