Arylation of [60]fullerene with Br₂/FeCl₃/PhH: Formation of C₅₈ derivatives via CO loss

Darwish, Adam D., Birkett, Paul R., Langley, G. John, Kroto, Harold W., Taylor, Roger and Walton, David R.M. (1997) Arylation of [60]fullerene with Br₂/FeCl₃/PhH: Formation of C₅₈ derivatives via CO loss. Fullerene Science and Technology, 5 (4), 705-726. (doi:10.1080/15363839708012227).

Abstract

Heating a mixture of [60]fullerene, bromine, ferric chloride and benzene under reflux for 24 h produces a range of phenylated [60]fullerene derivatives. The main product is C₆₀Ph₅H, but other components identified by mass spectrometry (and in some cases separated by HPLC) are: C₆₀Ph_n (n = 4, 6, 8, 10, 12), C₆₀Ph_nO₂ (n = 4, 6, 8, 10, 12), C₆₀Ph_nOH (n = 7, 9, 11), C₆₀Ph_nH₂ (n = 4, 10), C₆₀Ph₄H₄, C₆₀Ph₅H₃, C₆₀Ph_nO₂H (n = 5, 9), C₆₀Ph₄C₆H₄O₂, C₆₀Ph₉OH₃, and C₆₀Ph₁₁O₃H₂. In the corresponding reaction with toluene, the crude reaction mixture contained C₆₀(MeC₆H₄)₄ as a main product; C₆₀(ClC₆H₄)₅H was obtained from the reaction with chlorobenzene. Formation of these derivatives is believed to involve radical bromination of the fullerene, followed by electrophilic substitution of the halogenofullerene into the aromatic, accompanied in some case by hydrolysis, elimination and epoxide formation; oxidation may also introduce ketone/dioxetane functionality. The EI mass spectra of C₆₀Ph₄O₂ and C₆₀Ph₈O₂ show degradation to C₅₈Ph_n (n = 0 - 8), having structures believed to be related to the pseudofofullerenes C₆₈Ph_n (n = 0 - 8) reported recently. These results suggest that some derivatisations of fullerenes confer stability, due to the relief of strain.

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Contributors

Author: G. John Langley

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