Lanthanide Complexes Supported by a Trizinc Crown Ether as Catalysts for Alternating Copolymerization of Epoxide and CO2: Telomerization Controlled by Carboxylate Anions

A new family of heterometallic catalysts based on trimetalated macrocyclic tris(salen) ligands and rare-earth metals was prepared and structurally characterized. The LaZn3 system containing anionic ligands such as acetate plays a critical role in catalyzing the alternating copolymerization of cyclohexene oxide (CHO) and CO2 with a high proportion of carbonate linkages. Among the lanthanide metals, the CeZn3 system exhibits high catalytic activity with a turnover frequency (TOF) of over 370 h(-1). NMR analysis of the complex and end-group analysis of the polymer suggest that the acetate ligands are rapidly exchanged, not only among coordinated acetates, but also between coordinated acetates and added carboxylate anions. These unique properties make this the first example of telomerization for the copolymerization of CHO and CO2.