Theoretical Prediction of Fullerene Reactivity

Over the last a few decades, a great diversity of reactions have been developed to functionalize empty and endohedral fullerenes, the most common being Diels-Alder cycloaddition, 1, 3-dipolar cycloaddition, Bingel-Hirsch cycloaddition, [2 + 2] cycloaddition, free-radical reactions, and carbene reactions. Various fullerenes have been found to exhibit the different chemical reactivity and regioselectivity in these reactions, especially for the endohedral fullerenes with diverse encapsulated species. This chapter emphasizes the importance of theoretical prediction for the fullerene reactivity. The most favorable addition site among numerous nonequivalent carbon atoms can be unambiguously determined; meanwhile, essential physical factors including charge density, spin density, and pyramidalization angle have been demonstrated to be quite useful for predicting the potential addition sites on the fullerene surface.