Topological investigation of the reaction mechanism of glycerol carbonate decomposition by bond evolution theory

Abstract

The reaction mechanisms of the decomposition of glycerol carbonate have been investigated at the density functional theory level within the bond evolution theory. The four reaction pathways yield to 3-hydroxypropanal (TS1), glycidol (TS2a and TS2b), and 4-methylene-1,3-dioxolan-2-one (TS3). The study reveals non-concerted processes with the same number (four) of structural stability domains for each reaction pathway. For the two decarboxylation mechanisms, the two first steps are similar. They correspond to the cleavage of two single CO bonds to the detriment of the increased population of the lone pairs of two O atoms. These are followed, along TS1, by the transformation of a CO single bond into a double bond together with a proton transfer to create a CH bond. For TS2a and TS2b, the last step is a cyclization by CO bond formation. For the TS3 pathway, the first stage consists in the cleavage of a CH bond and the transfer of its electron population to both a proton and a C atom, the second step corresponds to the formation of an OH bond, and the last one describes the formation of a CC double bond. Moreover, the analysis of the energies, enthalpies, and free enthalpies of reaction and of activation leads to the conclusion that 3-hydroxypropanal is both the thermodynamic and kinetic product, independent of the method of calculation.