Theoretical investigation of the mechanism for the cycloaddition of CO2 to epoxides catalyzed by a magnesium(II) porphyrin complex.

The cycloaddition of CO2 to epoxides, catalyzed by Mg(TPP)/TBAI (TPP = tetraphenylporphyrin; TBAI = tetrabutylammonium iodide), was investigated using DFT methods. Epoxides with various substituents were studied to explore steric and electronic effects on the reaction mechanism. Computational results show that the cycloaddition proceeds according to a much easier mechanism in the presence of Mg(TPP) and TBAI than the mechanism that takes place when Mg(TPP) is used as the catalyst. A preference for the epoxide ring-opening to occur at the methine (Cα) or methylene (Cβ) carbon was noted. The ring-closing step leading to the formation of a five-membered carbonate is predicted to determine the reaction rate. For alkyl-substituted epoxides, the β pathway is favorable since steric factors are dominant; for epoxides with a strongly electron-donating group and styrene oxide, the reaction is mainly controlled by electronic factors and proceeds along the α pathway. When the epoxide has a strongly electron-withdrawing group (CF3), both steric and electronic effects play important roles. The calculated reactivity of epoxides with CO2 catalyzed by Mg(TPP)/TBAI is in good agreement with that observed experimentally.