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Novel addition in trifluoromethylation of [70]fullerene
journal contribution
posted on 2023-06-08, 00:37 authored by Adam D Darwish, Ala'a K Abdul-Sada, Anthony G Avent, Natalia Martsinovich, Joan M Street, Roger TaylorPyrolytic 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.
History
Publication status
- Published
Journal
Journal of Fluorine ChemistryISSN
0022-1139External DOI
Issue
9Volume
125Page range
1383-1391Pages
10.0Department affiliated with
- Chemistry Publications
Notes
AAS performent the adavanced analytical mass spectroscopy required for this paper and co-authored the paper in collaboation with the late RTFull text available
- No
Peer reviewed?
- Yes
Legacy Posted Date
2012-02-06Usage metrics
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