Theoretical mechanism study on the electrochemical benzylation of [60]fullerene derivatives

The electrochemical methodology is available for the functionalization of fullerenes. However, intricate and ambiguous issues remain to be identified for some electrochemical reactions. In this work, density functional theory (DFT) calculations reveal that the electron delocalization of C₆₀ in fullerobenzofuran (RF5) and the C₆₀-fused lactone (RL6) declines with the electron injection of electrochemistry, and clear active sites can be obtained to react with the electrophilic agent. Furthermore, the selectivity of the addition reaction depends on the O site, which is inclined to react with the C of C₆₀ after electron injection or the C of PhCH₂⁺, forming a new C-O bond.