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A series of 5,10,15,20‐tetrakis(2,3‐dichlorophenyl)porphyrinate complexes of manganese(III) [MnIII(T2,3DCPP)X] with six different axial ligands (X=NO3−, AcO−, IO3−, Br−, Cl−, HO−) were investigated as catalysts in the cycloaddition reactions of CO2 and styrene oxide (SO), under mild conditions, i. e., atmospheric pressure and 60 °C. [MnIIIT(2,3DCPP)IO3] showed the best catalytic performance, selectively producing the respective cyclic carbonate from diverse epoxides using tetrabutylammonium bromide as a nucleophile source. Mechanistic considerations were inferred from electronic spectra and spectrophotometric titrations, showing that there are a series of equilibriums involved in the formation of the catalytic active species. Stability constants for the proposed equilibrium models were determined using SQUAD software. A catalytic cycle has been proposed based on those observations.

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