Benzyne adds across a closed 5-6 ring fusion in C70:: Evidence for bond delocalization in fullerenes

Addition of benzyne to C-70 results in four isomeric monoadducts (compounds 1a-d) in a 42:35: 13:10 ratio as determined by H-1 NMR. These compounds were separated by repeated passes through HPLC columns. The major,isomer (1a) resulted from addition to the highly pyramidalized C1-C2 bond as shown by C-13 NMR and UV/vis spectroscopy. The structure of the C1-C2 adduct (1a) was confirmed by X-ray crystallography. The second isomer (1b) was assigned as an adduct to the C5-C6 bond on the basis of C-13 NMR and UV/vis spectroscopy. Compound 1c exhibited a C-13 spectrum consistent with an adduct to the C7 and C8 positions. The presence of sp(3) C-13 NMR resonances proved that the C7-C8 bond is still intact, making this the first identification of direct addition to a 5-6 ring fusion in a fullerene, and the first example of an adduct to a 5-6 ring fusion where the ring fusion bond remains intact. The fourth isomer (1d) displayed spectral data consistent with a compound with C-1 symmetry and is assigned as an adduct to the C7-C21 bond.