The synthesis and characterization of novel scandium and yttrium phosphasalen complexes is reported, where phosphasalen refers to two different bis(iminophosphorane) derivatives of the more ubiquitous salen ligands. The activity of the complexes as initiators for the ring-opening polymerization of cyclic esters is presented. The scandium complexes are inactive for lactide polymerization but slow and controlled initiators for e-caprolactone polymerization. The lack of activity toward lactide exhibited by these compounds is, probed, and a rare example of single-monomer insertion product, unable to undergo further reactions with lactide, is identified. In contrast, the analogous yttrium phosphasalen complex is a very active initiator for the ring Opening polymerization of rac-lactide (k(obs) = 1.5 x 10(-3) s(-1) at 1:500 [yttrium initiator]: [rac-lacticle], 1 M overall concentration Of lactide in THF at 298 K). In addition to being a very fast initiator, the yttrium complex also maintains excellent levels of polymerization control and a high degree of isoselectivity, with the probability of isotactic enchainment being P-i = 0,18 at 298 K.