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Novel addition in trifluoromethylation of 70 fullerene

Novel addition in trifluoromethylation of 70 fullerene
Novel addition in trifluoromethylation of 70 fullerene
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.
[70]fullerene, trifluoromethylation, addition patterns, fluorine nmr, mechanismray crystal-structures, fullerene derivatives, nmr characterization, c-70, silver, isomers, c70o, decomposition, fullerene, behavior
0022-1139
1383-1391
Darwish, A.D.
6f919f23-7ae3-49cf-8bf2-938a70987964
Abdul-Sada, A.K.
565c6808-e54c-4b87-ad95-1d84535389cc
Avent, A.G.
ef621cee-165f-4e31-8f28-ec83bba95618
Martsinovich, N.
54d1dc74-5970-4972-a2e3-9305bfadf37d
Street, J.M.
186366c0-692b-4236-bb93-e2a3b6e9395c
Taylor, R.
1abcd415-ae2c-4e95-a761-6948ce7f4d32
Darwish, A.D.
6f919f23-7ae3-49cf-8bf2-938a70987964
Abdul-Sada, A.K.
565c6808-e54c-4b87-ad95-1d84535389cc
Avent, A.G.
ef621cee-165f-4e31-8f28-ec83bba95618
Martsinovich, N.
54d1dc74-5970-4972-a2e3-9305bfadf37d
Street, J.M.
186366c0-692b-4236-bb93-e2a3b6e9395c
Taylor, R.
1abcd415-ae2c-4e95-a761-6948ce7f4d32

Darwish, A.D., Abdul-Sada, A.K., Avent, A.G., Martsinovich, N., Street, J.M. and Taylor, R. (2004) Novel addition in trifluoromethylation of 70 fullerene. Journal of Fluorine Chemistry, 125 (9), 1383-1391. (doi:10.1016/j.jfluchem.2004.04.009).

Record type: Article

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.

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More information

Published date: 1 September 2004
Keywords: [70]fullerene, trifluoromethylation, addition patterns, fluorine nmr, mechanismray crystal-structures, fullerene derivatives, nmr characterization, c-70, silver, isomers, c70o, decomposition, fullerene, behavior

Identifiers

Local EPrints ID: 20180
URI: http://eprints.soton.ac.uk/id/eprint/20180
ISSN: 0022-1139
PURE UUID: 65c664b3-dd7a-426a-8b4c-d0da2604e8a8

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Date deposited: 21 Feb 2006
Last modified: 15 Jul 2019 19:25

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Contributors

Author: A.D. Darwish
Author: A.K. Abdul-Sada
Author: A.G. Avent
Author: N. Martsinovich
Author: J.M. Street
Author: R. Taylor

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