The higher chlorofullerene, D3d-C60Cl30, and its dioxide, C2h-C60Cl30O2

• The highest chloride of the Isolated-Pentagon Rule fullerene C 60 , D 3d -C 60 Cl 30 , possesses a unique molecular structure featuring a drum-like carbon cage and the existence of π-aromatic systems, one trannulene ring and two benzenoid rings. Structural investigation of several solvates of D 3d -C 60 Cl 30 revealed a high rigidity of this molecule. Its oxidation occurs by an insertion of O atoms into the weakest C-C bonds under formation of intramolecilat diether, C 2h -C 60 Cl 30 O 2 , whereas the π-aromatic system remains nearly untouched. The highest chloride of the Isolated-Pentagon Rule (IPR) fullerene C 60 , D 3d -C 60 Cl 30 was isolated as solvates with toluene, o -dichlorobenzene, tetrachloroethane, and SbCl 5 . An X-ray crystallographic study of the solvates revealed a high rigidity of the D 3d -C 60 Cl 30 molecule due to the existence of isolated aromatic systems, two isolated benzenoid rings and one 18π trannulene ring. In two 15-membered chlorinated loops, ClC−CCl distances are elongated to 1.58 – 1.69 Å. An X-ray diffraction study of the oxidation product, C 60 Cl 30 O 2 , showed that the addition of both oxygen atoms occurs by an insertion into the weakest ClC−CCl bond under formation of intramolecular diether. In the C 2h -C 60 Cl 30 O 2 molecule, the ClC−CCl distances of the cleaved C−C bonds are 2.43 Å long whereas the π aromatic system remains nearly untouched.