Unexpected Periodicity in Cationic Group 5 Initiators for the Ring-Opening Polymerization of Lactones

epsilon-Caprolactone (epsilon-CL) adducts of cationic, amine tris(phenolate)-supported niobium(V) and tantalum(V) ethoxides initiate the ring-opening polymerization of lactones. The Ta(V) species prepared and applied catalytically herein exhibits higher activity in the ring-opening polymerization (ROP) of epsilon-caprolactone than the previously reported, isostructural Nb(V) complex, contradicting literature comparisons of Nb(V)- and Ta(V)-based protocols. Both systems also initiate the ROP of delta-valerolactone and rac-beta-butyrolactone, kinetic studies confirming retention of higher activity by the Ta congener. Polymerizations of rac-beta-butyrolactone and delta-valerolactone were previously unrealized under Group V- or Ta-mediated conditions, respectively, although the former has afforded only low molecular weight, cyclic poly-3-hydroxybutyrate. Cationic ethoxo-Nb(V) and -Ta(V) delta-valerolactone adducts are also reported, demonstrating the facility of delta-valerolactone as a ligand and the generality of the synthetic method. Both delta-valerolactone-bearing complexes initiate the ROP of epsilon-caprolactone, delta-valerolactone, and rac-beta-butyrolactone. Accordingly, we have elucidated trends in reactivity and investigated the initiation mechanism for such systems, the insertion event being predicated upon intramolecular nucleophilic attack on the coordinated lactone by the adjacent alkoxide moiety. This mechanism enables quantitative, stoichiometric installation of a single monomer residue distinct from the bulk of the polymer chain, and permits modification of polymer properties via both manipulation of the molecular architecture and tuning of the polymerization kinetics, and thus dispersity, through hitherto inaccessible independent control of the initiation event.