Synthesis, Structural Characterization of Substituted Phenoxyimine Based Ti(IV) Complexes for Ring Opening Polymerization and DFT Studies

Abstract

AbstractA series of 4 new titanium complexes bearing phenoxyimine ligands that differ in their steric and electronic properties have been synthesized and investigated for the polymerization of ethylene and rac‐lactide. X‐ray crystal structures of these catalysts reveal compounds 1–3 exhibit distorted octahedral geometry while complex 4 shows distorted trigonal bipyramidal. The substituents on the phenoxyimine framework have a profound influence on the catalytic activities of these compounds in the polymerization reactions. All four complexes afforded polylactide with a heterotactic bias in ring opening polymerization of rac‐lactide. In addition to this, density functional theory calculations using (B3LYP) with the 6‐311++G (d, p) basis set and no constraints were used while doing geometry optimizations and compared with experimental results. Hirshfeld surface analysis, MEP and Mulliken charge also reported an unexpected relationship between the nitrogen, oxygen on the ligands, titanium isopropoxide, and good relation between the experimental findings.