Polyesters are omnipresent in our everyday lives and their synthesis via eco-friendly methods is becoming a major challenge today. The co-polymerization of cyclic anhydrides and epoxides was first reported by...

The replacement of the imine functionality in the ubiquitous phenoxy-imine (FI) ligands by a more robust and donor N,N,N′-trisubstituted amidine function was examined and gave rise to the synthesis of five new phenoxy-amidine (FA) ligands (L1− L5). The solid-state structure of four proligands has been determined by X-ray diffraction analysis and showed that the amidine moiety is in a trans-configuration. The reaction of the phenol-amidine proligands with AlMe 3 afforded mononuclear (L1−L5)AlMe 2 (1a−5a). A similar alkane elimination route was used from ZnEt 2 and led to dinuclear [(L1−L5)ZnEt] 2 complexes (1b−5b) or to homoleptic (L2/L4) 2 Zn complexes (2b′, 4b′) depending on the metal/ligand ratio used. The structure of these complexes has been determined by NMR spectroscopy ( 1 H, 13 C, HMBC, HSQC, DOSY, and NOESY experiments) and X-ray diffraction study for seven of them. The crystal structure of the Al complexes showed FA ligands coordinated in a chelate fashion via the O atom of the aryloxy group and the imino-N atom, indicating that the amidine function has undergone trans−cis isomerization upon coordination. A similar chelating coordination mode was observed for the FA ligands with Zn metal ions. These complexes were used as initiators for the ring-opening polymerization of rac-lactide. FA−Zn complexes gave the best performance, affording polylactic acid with a narrow molecular weight distribution and heterotactic bias (Pr up to 0.75). Remarkably, some of these complexes were able to tolerate the presence of a large amount of lactic acid to the point of using it as a co-initiator during the polymerization reaction.