Heterodinuclear Zn(II), Mg(II) or Co(III) with Na(I) Catalysts for Carbon Dioxide and Cyclohexene Oxide Ring Opening Copolymerizations.

A series heterodinuclear catalysts, operating without co-catalyst, show good performances for the ring opening copolymerization (ROCOP) of cyclohexene oxide and carbon dioxide. The complexes feature a macrocyclic ligand designed to coordinate metals such as Zn(II), Mg(II) or Co(III), in a Schiff base 'pocket', and Na(I) in a modified crown-ether binding 'pocket'. The 11 new catalysts are used to explore the influences of the metal combinations and ligand backbones over catalytic activity and selectivity. The highest performance catalyst features the Co(III)Na(I) combination, [N,N'-bis(3,3'-triethylene glycol salicylidene)-1,2-ethylenediamino cobalt(III) di(acetate)]sodium (7), and it shows both excellent activity and selectivity at 1 bar carbon dioxide pressure (TOF=1590 h , >99 % polymer selectivity, 1 : 10: 4000, 100 °C), as well as high activity at higher carbon dioxide pressure (TOF=4343 h , 20 bar, 1 : 10 : 25000). Its rate law shows a first order dependence on both catalyst and cyclohexene oxide concentrations and a zeroth order for carbon dioxide pressure, over the range 10-40 bar. These new catalysts eliminate any need for ionic or Lewis base co-catalyst and instead exploit the coordination of earth-abundant and inexpensive Na(I) adjacent to a second metal to deliver efficient catalysis. They highlight the potential for well-designed ancillary ligands and inexpensive Group 1 metals to deliver high performance heterodinuclear catalysts for carbon dioxide copolymerizations and, in future, these catalysts may also show promise in other alternating copolymerization and carbon dioxide utilizations.