Novel addition in trifluoromethylation of [70]fullerene

Darwish, Adam D, Abdul-Sada, Ala'a K, Avent, Anthony G, Martsinovich, Natalia, Street, Joan M and Taylor, Roger (2004) Novel addition in trifluoromethylation of [70]fullerene. Journal of Fluorine Chemistry, 125 (9). pp. 1383-1391. ISSN 0022-1139

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Abstract

Pyrolytic trifluoromethylation of [70]fullerene with CF3CO2Ag at 300 degreesC results in the addition of up to 12 CF3 groups to the fullerene cage. Forty-six C-70(CF3)(n) derivatives (numbers in parentheses) were separated by two-stage high pressure liquid chromatography (HPLC) as follows: n = 2(2), 4(16), 6(9), 8(14) 10(5), some being characterised by F-19 NMR. The range of derivatives is much greater than for other [70]fullerene reactions, and as with [60] fullerene trifluoromethylation, no single derivative is dominant, indicating that kinetic stability mainly controls product formation. F-19 NMR spectra show most derivatives to be unsymmetrical, with combinations of quartets and septets (overlapping quartets) due to contiguous ('linear') addend arrays, having significantly different coupling constants of the 'terminal' quartets of between 9.1 and 17.7 Hz. These differences, together with those observed previously in trifluoromethylation of [60]fullerene are consistent with addition across both 6:6- and 5:6-ring junctions. Of the two C-70(CF3)(2) isomers, one has either C-s or C-2 symmetry, the other has C-1 symmetry, whilst the C-70(CF3)(4) derivatives fall into four categories: (i) symmetrical compounds (one gives only two singlets in the F-19 NMR); (ii) unsymmetrical compounds that show a 'linear' coupling sequence; (iii) unsymmetrical compounds having a remote pairs of adjacent groups; (iv) compounds having a coupled array of three CF3 groups, together with a remote group suggesting sterically-driven migration. The first evaluation of differential NMR couplings across 6:6- and 5:6-bonds in a fullerene has been made using C60F6 as a model. (C) 2004 Elsevier B.V. All rights reserved.

Item Type: Article
Additional Information: AAS performent the adavanced analytical mass spectroscopy required for this paper and co-authored the paper in collaboation with the late RT
Schools and Departments: School of Life Sciences > Chemistry
Depositing User: Adam Darwish
Date Deposited: 06 Feb 2012 19:56
Last Modified: 26 Mar 2012 09:52
URI: http://sro.sussex.ac.uk/id/eprint/23063
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