Description:
<jats:title>Abstract</jats:title><jats:p>Modulation of the reactivity of metallofullerenes is critical for production of metallofullerene derivatives with desired properties and functionalities. In this study, we investigate the effects of reduction and oxidation on the reactivity and regioselectivity in Diels–Alder reaction of metallofullerene La@C<jats:sub>82</jats:sub> by means of density functional theory calculations. Because of the enhanced electron‐deficiency characteristic upon oxidation, the oxidized metallofullerene exhibits higher thermodynamic and kinetic reactivity as compared with neutral La@C<jats:sub>82</jats:sub>. The regioselectivity in the reaction of La@C<jats:sub>82</jats:sub> with cylcopentadiene is remarkably changed after oxidation of the metallofullerene, which is explained in terms of the changes in the geometrical structure and the electronic structure of the metallofullerene. Quantitative analysis based on the activation‐strain model demonstrates that the low activation energy barrier for the reaction of the cation La@C<jats:sub>82</jats:sub><jats:sup>+</jats:sup> with cyclopentadiene originates from small strain energy and large interaction energy between the reactants. Energy decomposition analysis on the transition states of the reactions reveals that the exchange‐repulsion interaction energy is one of the critical factors that determine the kinetic reactivity of the metallofullerene. This study not only provides new theoretical insights on how to modulate the reactivity of metallofullerenes, but also offers guideline for future experimental synthesis of new metallofullerene derivatives.</jats:p>