Buried Volume Analysis for Propene Polymerization Catalysis Promoted by Group 4 Metals: A Tool for Molecular Mass Prediction

Abstract

A comparison of the steric properties of homogeneous single site catalysts for propene polymerization using the percentage of buried volume (% V Bur ) as molecular descriptor is reported. The % V Bur calculated on the neutral precursors of the active species seems to be a reliable tool to explain several experimental data related to the propene insertion and to the monomer chain transfer. Interestingly, a linear correlation between the buried volume calculated for a large set of neutral precursors and the energetic difference between propagation and termination steps calculated by density functional theory (DFT) methods is found for Group 4 metal catalysts. The “master curves” derived for Ti, Zr, and Hf confirm not only that the % V Bur is an appropriate molecular descriptor for the systems considered but also that it could be used as tool for a large computational screening of new ligands.