DFT insight into metals and ligands substitution effects on reactivity of phenoxy-imine catalysts for ethylene polymerization

The reaction mechanism of ethylene (ET) polymerization catalyzed by the phenoxy-imine (FI) ligands using DFT calculations was studied. Among five possible isomers, isomer A which has an octahedral geometry and a (cis-N/trans-O/cis-Cl) arrangement is the most stable pre-reaction Ti-FI dichloride complex. The isomer A can be activated by MAO to form the active catalyst and the active form was used for the study of the mechanism for Ti-FI. The second ethylene insertion was found to be the rate-determining step of the catalyzed ethylene polymerization. To examine the effect of group IVB transition metals (M = Ti, Zr, Hf) substitutions, calculated activation energies at the rate-determining step (E-a(RDS)) were compared, where values of E-a(RDS) of Zr < Hf < Ti agree with experiments. Moreover, we examined the effect of substitution on (O, X) ligands of the Ti-phenoxy-imine (Ti-1) based catalyst. The results revealed that E-a(RDS) of (O, N) > (O, O) > (O, P) > O, S). Hence, the (O, S) ligand has the highest potential to improve the catalytic activity of the Ti-FI catalyst. We also found the activation energy to be related to the Ti-X distance. In addition, a novel Ni-based FI catalyst was investigated. The results indicated that the nickel (II) complex based on the phenoxy-imine (O, N) ligand in the square-planar geometry is more active than in the octahedral geometry. This work provides fundamental insights into the reaction mechanism of M - FI catalysts which can be used for the design and development of M - FI catalysts for ET polymerization.