MnIII porphyrins: catalytic coupling of epoxides with CO2 under mild conditions and mechanistic considerations
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2019
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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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Carbon dioxide fixation, Homogeneous catalysis, Metalloporphyrins, Mild conditions, SQUAD
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MILANI, Jorge L. S. et al. MnIII porphyrins: catalytic coupling of epoxides with CO2 under mild conditions and mechanistic considerations. ChemCatChem, Weinheim, v. 11, n. 17, p. 4393-4402, 2019. DOI: 10.1002/cctc.201900745. Disponível em: https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/cctc.201900745. Acesso em: 29 set. 2023.