Electrochemically generated Lu3N@I-h-C-80 dianions react with the electrophile, PhCHBr2, to produce a methano derivative of Lu3N@I-h-C-80(CHC6H5) (1) with high regioselectivity. The compound was characterized by MALDI-TOF, NMR, and UV-vis-NIR absorption spectroscopy. Electrochemical characterization of this Lu3N@I-h-C-80(CHC6H5) derivative showed the typical irreversible reductive behavior of the pristine Lu3N@I-h-C-80, similar to those observed for Bingel adducts of Lu3N@Ih-C80. Using the same conditions, the reaction between Sc3N@I-h-C-80 dianions and PhCHBr2 was conducted for comparison. Unexpectedly, no nucleophilic reaction was observed, indicating that Sc3N@I-h-C-80 dianions are not reactive toward the electrophile. Theoretical studies for both dianionic Lu3N@T-h-C-80 and Sc3N@I-h-C-80 showed that the HOMO is more highly localized on the fullerene cage for [Lu3N@I-h-C-80](2-) and more localized on the inside cluster for [Sc3N@I-h-C-80](2-), providing an explanation for the drastically different reactivities observed.