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Department of Earth Sciences

Academic Staff

Publication details for Dr Valentina Erastova

Erastova, Valenitna, Rodríguez-Otero, Jesús, Cabaleiro-Lago, Enrique M. & Peña-Gallego, Ángeles (2011). A computational study of the mechanism of the unimolecular elimination of α,β-unsaturated aldehydes in the gas phase. Journal of Molecular Modeling 17(1): 21-26.

Author(s) from Durham

Abstract

The mechanism for the decarbonylation of (E)-2-butenal and (E)-2-methyl-3-pheny-2-propenal was studied with different levels of ab initio and DFT methods. Reactants, products and transition structures were optimized for two kinds of reaction channel: a one-step reaction which involves a three-membered cyclic transition state, and a two-step reaction which involves an initial four-membered cyclic transition state. According to our calculations, these two possible mechanisms entail similar energetic costs, and there are only small differences depending on the reactant. The elimination of (E)-2-methyl-3-pheny-2-propenal yields different products depending on the channel followed. Only one of the three possible one-step mechanisms leads directly to (E)-β-methylstyrene (the main product according to experiment). This fact is reasonably well reproduced by our results, since the corresponding transition state gave rise to the lowest activation Gibbs free energy.