Group 4 salalen complexes and their application for the ring-opening polymerization of rac-lactide

In this paper, we report the preparation and characterization of a series of unsymmetrical group 4 metal complexes based on ONNO salalen-type ligands. In these examples, the ligand is unsymmetrical with an amine and an imine nitrogen center. All complexes {except Hf(3)(OiPr)2} adopt a β-cis configuration in the solid state, which is also in agreement with solution-state NMR spectroscopic measurements. The complexes have been tested for the ROP of rac-lactide (both in solution and under melt conditions). Narrow polydispersities have been seen (1.07−1.82). The Ti(IV) complexes produce atactic PLA, whereas the Zr(IV) complexes form PLA with a heterotactic bias. Hf(IV) complexes have been shown to produce isotactic PLA with a Pm of 0.75. The kinetics for all initiators have been investigated and are discussed.