Isoselective Ring‐Opening Polymerization of <i>rac</i>‐Lactide Catalyzed by Sodium/potassium Tetradentate Aminobisphenolate Ion‐paired Complexes

Abstract

Two sodium/potassium tetradentate aminobisphenolate ion-paired complexes were synthesized and structurally characterized. These ion-paired complexes are efficient catalysts for the ring-opening polymerization of rac-lactide (rac-LA) in the presence of 5 equivalents BnOH as an initiator and the side reaction of epimerization can be suppressed well at low temperatures. The polymerizations are controllable, affording polylactides with desirable molecular weights and narrow molecular weight distributions; the highest molecular weight can reach 50.1 kg mol^-1 in this system, and a best isoselectivity of P_m =0.82 was achieved. Such polymerizations have rarely been reported for isoselective sodium/potassium complexes without crown ether as an auxiliary ligand. The solid structures suggest that BnOH can be activated by an interaction with the anion of sodium/potassium complex via a hydrogen bond and that the monomer is activated by coordination to sodium/potassium ion.