Isolation of two seven-membered ring C58 fullerene derivatives: C58F17CF3 and C58F18.

Fluorination of C60 at 550 degrees C leads to milligram quantities of two stable fullerene derivatives with 58-carbon cage structures: C58F18 and C58F17CF3. The compounds were characterized by mass spectrometry and fluorine nuclear magnetic resonance spectroscopy, and the data support a heptagonal ring in the framework. The resulting strain, which has hindered past attempts to prepare these smaller quasi-fullerenes, is mitigated here by hybridization change of some of the carbons in the pentagons from sp2 to sp3 because of fluorine addition.

Electrophilic aromatic substitution by the fluorofullerene C60F18.

The FeCl3-catalysed arylation of C60F18 gives tri-substituted compounds C60F15Ar3, where Ar=phenyl, 4-tolyl, 4-methoxyphenyl, 4-phenoxyphenyl, 4-chlorophenyl, 3,4-dichlorophenyl, 2-biphylenyl and 2-fluorenyl, together with some bis- and mono-substituted product. Bis-substitution was achieved with biphenylene and fluoranthene, and mono-substitution with biphenylene (2-position), pyrene (1-position), and naphthalene (1- and 2-positions); the tris-phenyl and tris-biphenylene derivatives are fluorescent. The 2-naphthyl substituent freely rotates at 328 K, whereas rotation of the 1-naphthyl substituent is prevented by interaction of the peri-hydrogen atom with fluorine.

Unusual addition patterns in trifluoromethylation of [60]fullerene.

From pyrolytic trifluoromethylation of [60]fullerene with CF3CO2Ag at 300 degrees C we have isolated ca. sixty C60(CF3)n isomers (numbers in parentheses) as follows: n = 2(1), 4(8), 6(13), 8(21), 10(11), 12(5), 14(4), twenty-one of which have been characterised by 19F NMR. Compounds with addition levels up to n = 20 have also been identified.

In the first proven SN2' fullerene reaction, both C3 and C1 C60F36 hydrolyse to C1 isomers of C60F35OH that eliminate HF to give epoxides C60F34O; C60F36O oxides are shown to be ethers, and a fourth isomer of C60F36 exists.

On standing in organic solvents containing traces of water, C3 and C1 isomers of C60F36 slowly convert to C1 isomers of C60F35OH. Both fluorofullerenols eliminate HF during EI mass spectrometry to give C60F34O epoxides, one fullerenol being much less stable than the other to the extent that the mass spectrum shows only the epoxide. Both C60F35OH isomers have C1 symmetry, one being identified by the remarkable linear relationship between chemical shifts in its 19F NMR spectrum and those in the spectrum of C1 C60F36; the spectrum of the other shows the pattern of C3 C60F36 rendered asymmetrical by the replacement of one F by OH.

[60]- and [70]Fullerenes are trifluoromethylated across 5:6-bonds.

Trifluoromethylation of [60]- and [70]fullerenes occurs across both 6:6- and 5:6-bonds giving unsymmetrical tetramethyl adducts having four contiguous CF3 groups; both fullerenes give bis adducts which do not involve 6:6-addition, and unsymmetrical hexa-adducts (with contiguous CF3 groups) are also obtained from [60]fullerene.