Structure and enhanced reactivity rates of the D5h Sc3N@C80 and Lu3N@C80 metallofullerene isomers: the importance of the pyracylene motif.

In this paper we report enhanced reactivity of the D(5h) isomers in comparison with the more common I(h) isomers of Sc(3)N@C(80) and Lu(3)N@C(80) toward Diels-Alder and 1,3-dipolar tritylazomethine ylide cycloaddition reactions. Also, the structure of the D(5h) isomer of Sc(3)N@C(80) has been determined through single-crystal X-ray diffraction on D(5h)-Sc(3)N@C(80).Ni(OEP).2benzene (OEP = octaethylporphyrin). The Sc(3)N portion of D(5h)-Sc(3)N@C(80) is strictly planar, but the plane of these four atoms is tipped out of the noncrystallographic, horizontal mirror plane of the fullerene by 30 degrees . The combination of short bond length and high degree of pyramidization for the central carbon atoms of the pyracylene sites situated along a belt that is perpendicular to the C(5) axis suggests that these are the sites of greatest reactivity in the D(5h) isomer of Sc(3)N@C(80). Consistent with the observation of higher reactivity observed for the D(5h) isomers, cyclic voltammetry and molecular orbital (MO) calculations demonstrate that the D(5h) isomers have slightly smaller energy gaps than those of the I(h) isomers. The first mono- and bis-adducts of D(5h) Sc(3)N@C(80) have been synthesized via 1,3-dipolar cycloaddition of tritylazomethine ylide. The NMR spectrum for the monoadduct 2b is consistent with reaction at the 6,6-ring juncture in the pyracylene unit of the D(5h) Sc(3)N@C(80) cage and is the thermodynamically stable isomer. On the other hand, monoadduct 2a undergoes thermal conversion to other isomeric monoadducts, and three possible structures are proposed.