Isolation and characterisation of symmetrical C60Me6, C60Me5Cl and C60Me5O2OH, together with unsymmetrical C60Me5O3H, C60Me5OOH, C60Me4PhO2OH, and C60Me12; fragmentation of methylfullerenols to C58

Abstract

Reaction of freshly prepared C₆₀Cl₆ (from chlorination of [60]fullerene by ICl in benzene) with methyllithium followed by hydrolysis and work-up including HPLC separation yields C_s symmetry C₆₀Me₆ (isostructural with C₆₀Br₆ and C₆₀Cl₆), together with unsymmetrical C₆₀Me₁₂ which is comprised of two of the motifs present in C₆₀Me₆ and must arise from the presence of a small amount of C₆₀Cl₁₂ in the C₆₀Cl₆. From the same reaction mixture we have also obtained C₆₀Me₅Cl [isostructural with C₆₀Ar₅Cl and C₆₀(OR)₅Cl], hydroxyepoxides [C₆₀Me₅O₂OH (symmetrical), C₆₀Me₅OOH and C₆₀Me₄PhO₂OH (both unsymmetrical)] and unsymmetrical C₆₀Me₅O₃H (a cage-opened ketone). The results provide further information concerning the addition patterns and mechanistic features of fullerene chemistry, show that methylated, arylated, alkoxylated and halogenated [60]fullerenes are isostructural, and that C₆₀Cl₆ also contains traces of C₆₀PhCl₅. Some of the compounds give exceptionally high intensities of the C₅₈⁺ fragmentation ion during EI mass spectrometry.