Electrochemical control of the regioselectivity in the exohedral functionalization of C_(60) the role of aromaticity

摘要

In this work we show that the regioselectivity of the Diels-Alder, 1,3-dipolar, and carbene cycloadditions to C_(60) changes from the usual [6,6] addition in neutral species to the [5,6] attack when the number of electrons added to the fullerenic cage increases. Changes in the aroma-ticity of the five- and six-membered rings of C_(60) during the reduction process provide a rationale to understand this regioselectivity change. Regioselectivity in the exohedral functionalization of fullerenes and endohedral metallofullerenes (EMFs) widely depends on the nature of the fullerene species and the metallic cluster encapsulated. This regioselectivity can change dramatically from the empty fullerenes to the EMFs.