Journal of Physical Chemistry A, Vol.112, No.35, 8154-8163, 2008
Regioselectivity in azahydro[60]fullerene derivatives: Application of general-purpose reactivity indicators
To attempt theoretical predictions of the regioselectivity pattern in molecules with multiple reactive sites, the energies of formation of all possible isomers are usually considered. This means that the computing becomes objective was to predict the regioselectivity highly demanding if high theoretical levels are used. The study ON in the reaction of hydrogen addition onto azahydro[60]fullerene C59Hn+1N (n = 0-4) systems using a new K reactivity indicator termed general-purpose reactivity indicator, Xi(kappa)(Delta N <= 0.alpha) proposed by Anderson et al. (J. Chem. Theor), Comput. 2007, 3, 358). Because Xi(kappa)(Delta N <= 0.alpha) combines the information from the electrostatic potential and the Fukui function, this indicator is a two-parameter model that depends on the atomic charges and Fukui values calculated. We used the gradient-corrected BLYP and BOP functionals to approximate the electronic density of the systems, and these densities were employed to determinate the parameters. In terms of regioselectivity, the preferential addition sites at every hydrogenation step on C59Hn+1N (n = 0-4) shows that 1,4-adducts are more stable than 1,2-adducts. However, we show that the multiple additions are only feasible up to a C59H5N (tetraddition) product. Consequently, the application of this indicator not only helps to avoid systematic computational studies by comparing energies of formation in several isomers--many of which are not Currently supported by experimental results-but also provides an insight of how the pattern of addition is achieved. Comparisons with traditional indicators show that the application of Xi(kappa)(Delta N <= 0.alpha) performs much better for predicting reactivity in the aza[60]fullerene derivatives studied.