When is the Bell–Evans–Polanyi principle fulfilled in Diels–Alder reactions of fullerenes?

Abstract

We present a theoretical study on the thermodynamic and kinetic reactivity of Diels–Alder cycloadditions to several empty fullerenes in order to investigate the relationship between reaction energies and energy barriers. The results show that fullerenes with large HOMO–LUMO gaps present good correlation coefficients. In all other cases, two factors are responsible for the lack of correlation. First, the formation of unexpected adducts which are not the ones resulting from a [4+2] addition and second the change in the electronic structure of some adducts due to the mixing of the ground state with excited states close in energy.