Heterodinuclear Mg(II)M(II) (M=Cr,Mn, Fe,Co, Ni,Cu and Zn) Complexes for the Ring Opening Copolymerization of Carbon Dioxide/Epoxide and Anhydride/Epoxide

The catalysed ring opening copolymerizations (ROCOP) of carbon dioxide/epoxide or anhydride/epoxide are controlled polymerizations that access useful polycarbonates and polyesters. Here, a systematic investigation of a series of heterodinuclear Mg(II)M(II) complexes reveals which metal combinations are most effective. The complexes combine different first row transition metals (M(II)) from Cr(II) to Zn(II), with Mg(II); all complexes are coordinated by the same macrocyclic ancillary ligand and by two acetate co-ligands. The complex syntheses and characterization data, as well as the polymerization data, for both carbon dioxide/cyclohexene oxide (CHO) and endo-norbornene anhydride (NA)/cyclohexene oxide, are reported. The fastest catalyst for both polymerizations is Mg(II)Co(II) which shows propagation rate constants (k_p) of 34.7 mM⁻¹ s⁻¹ (CO₂) and 75.3 mM⁻¹ s⁻¹ (NA) (100 °C). The Mg(II)Fe(II) catalyst also shows excellent performances with equivalent rates for CO₂/CHO ROCOP (k_p=34.7 mM⁻¹ s⁻¹) and may be preferable in terms of metallic abundance, low cost and low toxicity. Polymerization kinetics analyses reveal that the two lead catalysts show overall second order rate laws, with zeroth order dependencies in CO₂ or anhydride concentrations and first order dependencies in both catalyst and epoxide concentrations. Compared to the homodinuclear Mg(II)Mg(II) complex, nearly all the transition metal heterodinuclear complexes show synergic rate enhancements whilst maintaining high selectivity and polymerization control. These findings are relevant to the future design and optimization of copolymerization catalysts and should stimulate broader investigations of synergic heterodinuclear main group/transition metal catalysts.