Rearrangements involving the phenonium ion: a theoretical investigation

E del Río; M I Menéndez; R López; T L Sordo

doi:10.1021/ja0039132

Rearrangements involving the phenonium ion: a theoretical investigation

J Am Chem Soc. 2001 May 30;123(21):5064-8. doi: 10.1021/ja0039132.

Authors

E del Río¹, M I Menéndez, R López, T L Sordo

Affiliation

¹ Departamento de Química Física y Analítica, Facultad de Química, Universidad de Oviedo, C/Julián Clavería, 8, 33006 Oviedo, Principado de Asturias, Spain.

PMID: 11457336
DOI: 10.1021/ja0039132

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.