Understanding and predicting the effect of epoxide structure on the rate of polymerization in epoxide/CO<sub>2</sub> ring opening copolymerization catalysis is a long-standing challenge. Here, a known highly active Co(III)K(I) catalyst is used to investigate the influences of six different epoxides' binding strengths on their rates of copolymerization. Since calculations and experiments indicate that studying the catalytically relevant Co(III)-epoxide adduct directly is experimentally challenging, epoxide-catalyst binding interactions are quantified using a Co(II)K(I) complex to model the key catalytic intermediate. Epoxide-catalyst coordination is investigated using UV-vis spectroscopy titrations which provide fast and effective determination of association or binding constants. The epoxide-catalyst equilibrium constants show a clear exponential correlation with copolymerization rates and a new catalyst performance linear free energy relationship is revealed. Epoxides exhibiting stronger catalyst binding constants show higher copolymerization rates. The structure-activity correlation is consistent with the polymerization kinetics, mechanism and DFT calculations. Both the methods to investigate epoxide-catalyst coordination and the linear free energy relationship are shown to apply to the series of six epoxides and a second Co(III)K(I) catalyst. These structure-performance relationships are likely applicable to other transition metal catalysts and should expedite future epoxide and catalyst selection to make useful poly(carbonate) materials.
