Nonclassical C 86 and C 88 Chlorofullerenes via Complex Chlorination-Promoted Skeletal Transformations of IPR Isomers of C 88 and C 96 .

Upon high-temperature (340-360 °C) chlorination with VCl 4 , an isolated-pentagon-rule (IPR) C 2 -C 88 (33) fullerene is just chlorinated to C 88 (33)Cl 22 and C 88 (33)Cl 28 , but a VCl 4 /SbCl 5 mixture promotes a five-step cage transformation to nonclassical C 86 ( NC 2)Cl 30 with two heptagons and five pairs of fused pentagons. Another chlorination-promoted seven-step transformation of an IPR fullerene removes as many as four C2 fragments from C 96 to give a nonclassical C 88 ( NC 1)Cl 30 with cage heptagon and six fused pairs of pentagons. We discuss the driving forces behind the observed transformations and probable detailed pathways thereof.