Experimental and Theoretical Approach to Variable Chlorination-Promoted Skeletal Transformations in Fullerenes: The Case of C102

The first example of three alternative chlorination-promoted skeletal transformation pathways in the same fullerene cage is presented. Isolated-pentagon-rule (IPR) C102(19) undergoes both Stone–Wales rotations to give non-IPR #283794C102Cl20 and C2 losses to form nonclassical C98 and non-IPR C96. X-ray structural characterization of the transformation products and a theoretical study of their formation pathways are reported.