Introduction of halogen electron withdrawing atoms (chloro and fluoro) in the ortho position of the aryl groups of meso-tetraphenylporphyrin manganese(III) complexes increased their activity as catalysts in the reaction of carbon dioxide with epoxides, when compared with the meso-tetraphenylporphyrin manganese(III) counterpart, even in the absence of co-catalysts. In the polymerization reaction of carbon dioxide and cyclohexene oxide, almost ten-fold increase of the TOF was observed when 5,10,15,20-tetra(2,6-dichlorophenyl)porphyrinatomanganese(III) acetate or 5,10,15,20-tetra(2,6-difluorophenyl)porphyrinatomanganese(III) acetate complexes were used as catalysts. Under similar conditions, when terminal epoxides were used as substrates, the selective cycloaddition of CO2 with styrene oxide, epichlorohydrin, propylene oxide, and 1,2-epoxytetradecane yielded exclusively the corresponding cyclic carbonates (conversion 6-98%). (C) 2016 Published by Elsevier B.V.