Chemical reactivity in nucleophilic cycloaddition to C70: vibronic coupling density and vibronic coupling constants as reactivity indices.
The chemical reactivity in nucleophilic cycloaddition to C70 is investigated on the basis of vibronic (electron-vibration) coupling density and vibronic coupling constants. Because the e1″ LUMOs of C70 are doubly degenerate and delocalized throughout the molecule, it is difficult to predict the regioselectivity by frontier orbital theory. It is found that vibronic coupling density analysis for the effective mode as a reaction mode illustrates the idea of a functional group embedded in the reactive sites. Furthermore, the vibronic coupling constants for localized stretching vibrational modes enable us to estimate the quantitative reactivity. These calculated results agree well with the experimental findings. The principle of chemical reactivity proposed by Parr and Yang is modified as follows: the preferred direction is the one for which the initial vibronic coupling density for a reaction mode of the isolated reactant is a minimum.
Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan.
Naoki
N
Haruta
Tohru
T
Sato
Kazuyoshi
K
Tanaka