The origin of the experimentally known preference for [6,6] bonds in cycloaddition reactions involving C60 has been computationally explored. To this end, we examined the reactions of 1,3-dienes with fullerene (C60) in the context of an approach to open a large orifice on the fullerene framework by using the activation model of reactivity in combination with the energy analysis method. In this study, the effect of the alkali metal of Li+, Na+, and K+ as an encapsulated element was investigated on the kinetic and thermodynamic behaviors of the Diels–Alder (DA) process. Our calculations indicated that encapsulated Na+ and K+ cations are located close to the center of the C60 molecule; however, encapsulated Li+ is displaced from the center, which leads to a higher reactivity for Li+@C60 in DA cycloaddition reaction in the gas phase. Also, benzene as a non-polar solvent affects the DA reactions greater than water as a polar solvent. Different analyses show that solvent changes the catalysis reaction performance, in which a greater efficiency was obtained for K+ in the solvent in comparison with other alkali ions because of a facilitated mechanism of electron transfer.

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