Theoretical Studies of Substituted Naphthylcarbinyl Cations and Associated Correlation Analysis

Abstract

Minimal basis set ab initio calculations are performed on naphthalenes and naphthalenecarbinyl cations substituted by CH3, F, CF3, CN, CH3O, NH2, and NO2. Suitable substitution reverses the inherent stability of a 1-naphthylcarbinyl cation over a 2-naphthylcarbinyl cation. Homodesmotic stabilization energies are correlated according to a modified Dewar-Grisdale equation as well as Taft's dual substituent parameter (DSP) equation, and the results are compared with published experimental data and corresponding treatments for benzyl cations. © 1982, American Chemical Society. All rights reserved.