title: Reactivity of metallic nitride endohedral metallofullerene anions: electrochemical synthesis of a Lu3N@Ih-C80 derivative.
abstract: Electrochemically generated Lu(3)N@I(h)-C(80) dianions react with the electrophile, PhCHBr(2), to produce a methano derivative of Lu(3)N@I(h)-C(80)(CHC(6)H(5)) (1) with high regioselectivity. The compound was characterized by MALDI-TOF, NMR, and UV-vis-NIR absorption spectroscopy. Electrochemical characterization of this Lu(3)N@I(h)-C(80)(CHC(6)H(5)) derivative showed the typical irreversible reductive behavior of the pristine Lu(3)N@I(h)-C(80), similar to those observed for Bingel adducts of Lu(3)N@I(h)-C(80). Using the same conditions, the reaction between Sc(3)N@I(h)-C(80) dianions and PhCHBr(2) was conducted for comparison. Unexpectedly, no nucleophilic reaction was observed, indicating that Sc(3)N@I(h)-C(80) dianions are not reactive toward the electrophile. Theoretical studies for both dianionic Lu(3)N@I(h)-C(80) and Sc(3)N@I(h)-C(80) showed that the HOMO is more highly localized on the fullerene cage for [Lu(3)N@I(h)-C(80)](2-) and more localized on the inside cluster for [Sc(3)N@I(h)-C(80)](2-), providing an explanation for the drastically different reactivities observed.
authors.affiliation: Department of Chemistry, University of Texas at El Paso, El Paso, Texas 79968, USA.
authors.forename: Fang-Fang
authors.initials: FF
authors.lastname: Li
authors.forename: Antonio
authors.initials: A
authors.lastname: Rodríguez-Fortea
authors.forename: Josep M
authors.initials: JM
authors.lastname: Poblet
authors.forename: Luis
authors.initials: L
authors.lastname: Echegoyen
mesh_terms: D000838:Anions / Q000737:chemistry; D004563:Electrochemistry; D037741:Fullerenes / Q000737:chemistry*; D008187:Lutetium / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009570:Nitriles / Q000737:chemistry*
chemical_list: D000838:Anions; D037741:Fullerenes; D009570:Nitriles; D008187:Lutetium