title: Rearrangements involving the phenonium ion: a theoretical investigation.
abstract: Rearrangements involving the phenonium ion were investigated by means of a B3LYP/6-311G(d,p) study in which the effect of solvent has been incorporated by using a PCM solvation model. A rationalization of the whole set of experimental facts reported both in the gas phase and in solution was possible thanks to the characterization of protonated benzocyclobutene as a minimum energy structure and, particularly, to the important preferential stabilization in solution of the TS for the isomerization of the phenonium ion to the alpha-methylbenzyl ion, which reduces the Gibbs energy barrier of 26.6 kcal/mol for this process in the gas phase to a more accessible one of 18.7 kcal/mol in solution.
authors.affiliation: Departamento de Química Física y Analítica, Facultad de Química, Universidad de Oviedo, C/Julián Clavería, 8, 33006 Oviedo, Principado de Asturias, Spain.
authors.forename: E
authors.initials: E
authors.lastname: del Río
authors.forename: M I
authors.initials: MI
authors.lastname: Menéndez
authors.forename: R
authors.initials: R
authors.lastname: López
authors.forename: T L
authors.initials: TL
authors.lastname: Sordo