Unconventional Stereoerror Formation Mechanisms in Nonmetallocene Propene Polymerization Systems Revealed by DFT Calculations.

An unconventional mechanism for the stereoerror formation in propene polymerization catalyzed by C 1 -symmetric salalen-M systems (M = Zr, Hf) is suggested by DFT calculations. While propagation happens with the ligand in its fac-mer conformation, a change of ligand wrapping mode from fac-mer to fac-fac is the main source of the lower stereoselectivities obtained with Zr and Hf. This is different for the Ti analogues, where the ligand fac - mer wrapping mode does not play a role. Activation strain analysis indicates that the preference for a chain stationary mechanism of the Zr/Hf species is due to the energy required to distort the reactants (Δ E Strain ) rather than to their mutual interaction (Δ E Int ) .