Synthesis and structures of C60 fullerene chlorides

Systematic study of chlorination of fullerene C-60 with inorganic chlorides SbCl5, VCl4, MoCl5, and KICl4 was carried out. Higher chlorofullerenes, viz., T-h-C6oCl24, C60Cl28, C-2-C60Cl30, and D-3d-C60Cl30, can be prepared depending on the. temperature and time of chlorination. The molecular and crystal structures of C(60)Cl(24)center dot VOCl3, C(60)Cl(30)center dot 2CS(2), and C60Cl30O1.22 were determined by single-crystal X-ray diffraction. Fullerenes C60Cl28 and C-2-C60Cl30 were shown to be only kinetically stable, whereas D-3d-C60Cl30 is a thermodynamically stable product. Transformations of less chlorinated fullerenes into more chlorinated products are accompanied by substantial changes in the addition patterns.