A Computational Study on the Chemical Fixation of Carbon Dioxide with Epoxide Catalyzed by LiBr Salt

Abstract

The chemical fixation of carbon dioxide with 2,3-epoxypropyl phenyl ether catalyzed by LiBr salt to produce a five-membered cyclic carbonate, 4-(phenoxymethyl)-1,3-dioxolan-2-one, has been extensively investigated at the B3LYP density functional level of theory. The solvent effects have been studied by means of a PCM model. All possible pathways are examined, and their corresponding energetics are demonstrated. Our results reveal that the overall reaction comprises three main steps: epoxide ring-opening, carbon dioxide insertion, and ring-closure of cyclic carbonate, none of which contains significantly large barriers. On the basis of the computed free energies of activation, the rate-determining step can be the ring-opening of epoxide or the ring-closure of cyclic carbonate with variation in the reaction conditions in N-methylpyrrolidinone (NMP) solvent. Our calculations indicate that path 2 is more favorable than path 1 in the gas phase, while both of them exist possibly in NMP solvent. The overall reaction is exothermic. Furthermore, the free energy profiles of all reaction pathways along the minima energy path in the gas phase and in NMP solvent were obtained and compared. It is shown that NMP solvent does not change the general trends for the reaction potential energy surfaces.