Lactide polymerization using a sterically encumbered, flexible zinc complex

Abstract

4-(tert-Butyl)-2-trityl-6-(di-(2-picolyl)amine)phenol, LH, was prepared from paraformaldehyde, 4-(tert-butyl)-2-tritylphenol and di-(2-picolyl)amine. Reaction with Zn(N(SiMe3)2)2 gave LZnN(SiMe3)2. The complex was shown by X-ray diffraction study, variabletemperature NMR and DFT calculations to coordinate only one pyridine ligand, which allows for fast and facile complex isomerisation. LZnN(SiMe3)2 was active in rac-lactide polymerization, but in contrast to previous complexes of this type did not show any evidence for isotactic monomer enchainment via a catalytic-site mediated chain-end control mechanism. Addition of alcohol led to increased activity, but the complex was unstable in the presence of free alcohol.