Effects of Solvents on Reaction Products: Synthesis of Endohedral Metallofullerene Oxazoline and Epoxide

Abstract

Herein, we performed the reactions of M3N@I h-C80 (M = Sc and Lu) with the methanol (CH3OH) solution of TBAOH (note that both CH3O– and OH– are nucleophiles) in benzonitrile (PhCN) and dimethylformamide, respectively. It is found that OH– ions rather than CH3O– ions selectively attacked the fullerene cage to form the M3N@C80 ––O– intermediate. Although the fullerene cage is initially attacked by OH– in both PhCN and DMF solvents, the products are quite different. In PhCN, two isomeric Sc3N@I h-C80 fullerooxazoline heterocyclic products (1 and 2) were synthesized. Whereas, in DMF, an epoxide of Lu3N@I h-C80 (3) was obtained. The preference for fullerooxazoline formation over that of fullerene epoxy in PhCN is well explained by density functional theory calculations. Plausible reaction mechanisms for the formation of metallofullerene oxazoline and epoxide were proposed based on the experimental and theoretical results.

Reactivity of Open-Shell Metallofullerene Anions: Synthesis, Crystal Structures, and Electrochemical Properties of Benzylated Gd@C2v-C82

“…The DPC molecules were found to form a V-shaped structure when combined with 2a and 2b, with the angle between the DPC molecules being 64.9° and 64.8°, respectively. The arrangement of these two molecules is very similar to other reported structures [51][52][53][54]. In 2a•2DPC, the distances between the centroid of the C82 cage and the central five-membered rings of DPC molecules are 7.361 Å and 7.394 Å, while they are 7.439 Å and 7.474 Å in 2b•2DPC.…”