Trimetallic nitride endohedral metallofullerenes: Reactivity dictated by the encapsulated metal cluster

The first derivatives of Y3N@C-80 have been synthesized and fully characterized. 1,3-Dipolar cycloaddition of N-ethylazomethine ylide yielded mainly the pyrrolidine monoadduct of the icosahedral (I-h) symmetry cage exclusively at a [6,6] double bond. The same regioselectivity on a [6,6] double bond was observed when the endohedral compound was cyclopropanated with diethyl bromomalonate. These results are in pronounced contrast to those observed for icosahedral symmetry Sc3N@C-80, for which all reported derivatives add completely regioselectively to [5,6] double bonds. H-1 NMR, C-13 NMR, and HMQC spectroscopy revealed that the addition pattern on Y3N@C-80 resulted in a pyrroliclinofullerene derivative with unsymmetric pyrrolidine carbons and symmetric geminal protons. The cyclopropanated monoadduct exhibited symmetric ethyl groups on the malonate, consistent with regioselective addition at a [6,6] double bond. Attempts to perform the same cyclopropanation reaction on (I-h) Sc3N@C-80 failed to yield any identifiable products. These observations clearly indicate that the reactivity of trimetallic nitride endohedral metallofullerenes toward exohedral chemical functionalization is profoundly affected and effectively controlled by the nature of the enclohedral metal cluster.