The reduction of 3He@C60 and 3He@C70 by lithium metal to give solutions of the corresponding hexaanions in THF-d 8 has been achieved under gentle conditions, at subambient temperatures, without sonication, by capitalizing on the ability of corannulene (1) to serve as an efficient electron carrier between the lithium metal and the solid fullerenes, which are virtually insoluble in the reaction medium. The 3He inside the C60 hexaanion is found to be more strongly shielded (by nearly 20 ppm!) than any previously reported 3He in a fullerene [δ(3He@C60 6-) = −48.7 ppm, relative to dissolved 3He gas in the solution], whereas the 3He inside the C70 hexaanion is actually deshielded [δ(3He@C70 6-) = +8.3 ppm], resonating at nearly 15 ppm lower field than any previously reported 3He in a fullerene. These results stand in complete accord with earlier predictions that the magnetic properties of C60 and C70 would be altered dramatically, and in opposite directions, by reduction of the fullerenes to their hexaanions. The phenomenal ability of C60 6- to shield an endohedral 3He from a powerful external magnetic field provides the most compelling evidence to date for the ability of electrons to move freely about the surface of a spheroidal π-system.

Stable π-conjugated anions are formed in the reaction of π-conjugated systems with alkali metals. Reactivity, aromatic properties and aggregation of the anions are described.