Aluminium complexes of phenoxy-azo ligands in the catalysis of rac-lactide polymerisation.

Abstract

Fourteen new phenoxy-azo aluminium complexes comprising two series, namely, dimethyl{phenoxy-azo}aluminium complexes 1a-7a and monomethyl{phenoxy-azo}aluminium complexes 1b-7b, were successfully synthesised and characterised. The molecular structure of complex 4a, determined using X-ray diffraction analysis, displayed a distorted tetrahedral geometry. The 1H NMR spectrum of complex 5b revealed fluxional behaviour caused by isomeric transformation that occurs in the solution at room temperature. The activation parameters determined by lineshape analysis of variable-temperature 1H NMR spectra in toluene-d8 are as follows: ΔH‡ = 70.05 ± 1.19 kJ mol-1, ΔS‡ = 21.78 ± 3.58 J mol-1 K-1 and ΔG‡ (298 K) = 63.56 ± 0.11 kJ mol-1. All aluminium complexes are active initiators for the ring-opening polymerisation of rac-lactide, and the polymerisations proceeded in a controlled manner and were living. In comparison, the catalytic activity of the dimethyl{phenoxy-azo}aluminium complexes was insignificantly different from that of the corresponding monomethyl{phenoxy-azo}aluminium complexes. The steric factor of the ortho-phenoxy substituent was observed to exert a decelerating effect on the catalytic rate. Kinetic investigations revealed first-order dependency on both monomer and initiator concentrations. Comparative catalytic investigations conducted on phenoxy-azo aluminium and phenoxy-imine aluminium complexes revealed that the former complexes exhibited lower catalytic activity.