Radical Trifluoromethylation of Sc3N@C80

Abstract

The addition of CF3 radicals to both the Ih and D5h cage-isomers of Sc3N@C80 by high-temperature reaction of the metallic nitride fullerenes with gaseous CF3I has resulted in the isolation of Sc3N@(C80-Ih)(CF3)2 and Sc3N@(C80-D5h)(CF3)2, which have idealized C2 and Cs symmetry, respectively. Both new compounds were characterized by 19F NMR and electronic absorption spectroscopy, mass spectrometry, and quantum-chemical calculations at the DFT level of theory, and the Ih cage derivative was also characterized by cyclic voltammetry. The results indicate that both compounds have a p-C6(CF3)2 hexagon with endohedral Sc atoms bonded to the sp2 cage C atoms para to the sp3 cage C(CF3) atoms.