Synthesis and structures of C60 fullerene chlorides

Systematic study of chlorination of fullerene C60 with inorganic chlorides SbCl5, VCl4, MoCl5, and KICl4 was carried out. Higher chlorofullerenes, viz., Th-C60Cl24, C60Cl28, C2-C60Cl30, and D3d-C60Cl30, can be prepared depending on the temperature and time of chlorination. The molecular and crystal structures of C60Cl24⋅VOCl3, C60Cl30⋅2CS2, and C60Cl30O1.22 were determined by single-crystal X-ray diffraction. Fullerenes C60Cl28 and C2-C60Cl30 were shown to be only kinetically stable, whereas D3d-C60Cl30 is a thermodynamically stable product. Transformations of less chlorinated fullerenes into more chlorinated products are accompanied by substantial changes in the addition patterns.