title: A computational study of the mechanism of the unimolecular elimination of α,β-unsaturated aldehydes in the gas phase.
abstract: The mechanism for the decarbonylation of (E)-2-butenal and (E)-2-methyl-3-phenyl-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-phenyl-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.
authors.affiliation: Departamento de Química Física, Facultade de Química, Universidade de Santiago de Compostela, Avda. das Ciencias s/n., 15782 Santiago de Compostela, Spain.
authors.forename: Valentina
authors.initials: V
authors.lastname: Erastova
authors.forename: Jesús
authors.initials: J
authors.lastname: Rodríguez-Otero
authors.forename: Enrique M
authors.initials: EM
authors.lastname: Cabaleiro-Lago
authors.forename: Angeles
authors.initials: A
authors.lastname: Peña-Gallego
mesh_terms: D000447:Aldehydes / Q000737:chemistry*; D005740:Gases / Q000737:chemistry*
chemical_list: D000447:Aldehydes; D005740:Gases