Rearrangements involving the phenonium ion:: A theoretical investigation

被引：32

作者：

del Río, E ^{[1
]}

Menéndez, MI ^{[1
]}

López, R ^{[1
]}

Sordo, TL ^{[1
]}

机构：

[1] Univ Oviedo, Fac Quim, Dept Quim Fis & Analit, Oviedo 33006, Asturias, Spain

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2001年 / 123卷 / 21期

关键词：

D O I：

10.1021/ja0039132

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

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.

引用

页码：5064 / 5068

页数：5

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