Chloro- and Trifluoromethyl Derivatives of a Pentagon-Fused C₆₀: ¹⁸¹⁰C₆₀Cl₂₄, ¹⁸¹⁰C₆₀Cl₂₀, and ¹⁸¹⁰C₆₀(CF₃)₁₄

Abstract

The carbon cage of I h -C60, obeying the isolated-pentagon rule (IPR), can be transformed to the non-IPR D 2h -1810C60 cage via two successive Stone–Wales rearrangements in the course of high-temperature chlorination of C60 with SbCl5. Two chloro derivatives, C 2v -1810C60Cl24 and C 2v -1810C60Cl20, have been isolated by high-performance liquid chromatography (HPLC). High-temperature trifluoromethylation of the chlorination products with CF3I, followed by HPLC separation, afforded a non-IPR CF3 derivative, C s -1810C60(CF3)14. Structural elucidation of the isolated compounds revealed that all eight sites of pentagon–pentagon fusions on the carbon cage are preferentially occupied by Cl atoms or CF3 groups. According to density functional theory calculations, chloro and CF3 derivatives of 1810C60 are more stable than the isomeric derivatives of 1809C60 or IPR 1812C60, possessing respectively four or no sites of pentagon fusion in their carbon cages.