Polylactide (PLA) is an attractive polymeric material due to its origin from annually renewable resources and its biodegradability. The ring-opening polymerization (ROP) of lactide initiated by Lewis acidic and oxophilic metal-based catalysts constitutes the method of choice to access PLA in a controlled and stereoselective manner. The design and synthesis of ligand-supported metal complexes to act as effective ROP initiators of lactide monomers have been the subject of numerous investigations over the past decades. In view of their oxophilic nature, well-defined group 4 metal complexes supported by polydentate supporting ligands have appeared as active initiators for lactide ROP. This perspective summarizes various classes of structurally well-defined group 4 metal initiators developed for lactide ROP. It also provides observed trends regarding their catalytic performance. Whenever appropriate and possible, catalyst structure-ROP performance (i.e. activity, control and stereoselectivity) relationships are rationalized.

The old switcheroo! The ring‐opening polymerization activity towards meso‐lactide significantly differs when cerium complexes with two bis(phenolate) ligands (OSSO type) change their oxidation state from +4 to +3. This switch can be performed in situ by chemical reduction or oxidation of the catalyst. The redox switching is possible up to three times in a row. PLA=polylactide.

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We developed a salt-free reduction of WCl6 using 1-methyl-3,6-bis(trimethylsilyl)-1,4-cyclohexadiene (MBTCD) in toluene to give a low-valent trinulcear tungsten complex involving W(II) and W(III) centers, while in the presence of redox active ligands such as α-diketone and α-diimine the same reduction produced W(IV) complexes with the corresponding redox-active ligands, (α-diketone)WCl4 and (α-diimine)WCl4. A W(VI) complex with two α-diketone ligands, (α-diketone)2WCl2, was found to be synthetically equivalent to low-valent W(IV) species that trapped azopyridine to give (α-diketone)WCl2(azopyridine).

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