Two successive C2 losses from C86 fullerene upon chlorination with the formation of non-classical C84Cl30 and C82Cl30.

High-temperature chlorination of a fullerene C86 with VCl4 afforded non-classical C84Cl30 and C82Cl30 containing one and two heptagons, respectively, in the carbon cages. Two types of C2 losses, which differ in the final arrangements of separate or fused pentagons, can occur successively in either order, producing rather flat or concave regions on the shrinked carbon cage. In the chlorination-promoted skeletal transformation of C86 (isomer no. 16) with the loss(es) of C2 units, the structures of the starting, intermediate, and final compounds were all revealed unambiguously by X-ray single crystal diffraction.