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Reactivity of metallic nitride endohedral metallofullerene anions: electrochemical synthesis of a Lu3N@Ih-C80 derivative
Authors:Li Fang-Fang  Rodríguez-Fortea Antonio  Poblet Josep M  Echegoyen Luis
Institution:Department of Chemistry, University of Texas at El Paso, El Paso, Texas 79968, USA.
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.
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