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DOI: 10.1039/A900313D (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 2, 1999, 1475-1480

The 3He NMR spectra of C60F18 and C60F36; the parallel between hydrogenation and fluorination

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Olga V. Boltalina, Michael Bühl, Anthony Khong, Martin Saunders, Joan M. Street and Roger Taylor

Abstract

Both i[hair space] 3HeC60F18 and i[hair space] 3HeC60F36 have been prepared by fluorinating i[hair space] 3HeC60. The 3He NMR spectrum of i[hair space] 3HeC60F18 shows a single line at –16.66 ppm, very close to the value of –16.45 ppm, recorded previously for the isostructural i[hair space] 3HeC60H18. Density functional calculations afford values of –15.0 and –16.2 ppm for the hydrogenated and fluorinated compounds, respectively. The 3He NMR spectrum of i[hair space] 3HeC60F36 consists of two almost coincident lines (intensity ratio of ca. 3∶1), at –10.49 and –10.52 ppm, attributable respectively to the C3 and T isomers shown previously to be the components (also in ca. 3∶1 ratio) of C60F36. The spectrum is similar to that (lines at –7.8 and –7.9 ppm in a similar ratio) recorded previously for i[hair space] 3HeC60H36, and provides compelling evidence that C60H36 also consists of a mixture of C3 (major) and T (minor) isomers. The observed ca. 2–3 ppm upfield shift of the spectral lines for the C60F36 isomers compared to those for the C60H36 isomers is reproduced by both density functional and SCF calculations. The C3 isomer involved has been identified by comparison of its 2D 19F NMR spectrum with that for the T isomer. It is not the isomer calculated to be the most stable one, and its formation is believed to be favoured by contiguous activation of double bonds adjacent to those that have already undergone addition.

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