ASAP J. Am. Chem. Soc., ASAP Article, 10.1021/ja8041614

Synthesis and X-ray or NMR/DFT Structure Elucidation of Twenty-One New Trifluoromethyl Derivatives of Soluble Cage Isomers of C76, C78, C84, and C90

Ivan E. Kareev,*†§ Alexey A. Popov,*‡ Igor V. Kuvychko,¶ Natalia B. Shustova,¶ Sergey F. Lebedkin,§ Vyachevslav P. Bubnov,† Oren P. Anderson,¶ Konrad Seppelt,# Steven H. Strauss,*¶ and Olga V. Boltalina*¶

Abstract:
Adding 1% of the metallic elements cerium, lanthanum, and yttrium to graphite rod electrodes resulted in different amounts of the hollow higher fullerenes (HHFs) C76-D2(1), C78-C2v(2), and C78-C2v(3) in carbon-arc fullerene-containing soots. The reaction of trifluoroiodomethane with these and other soluble HHFs at 520−550 °C produced 21 new C76,78,84,90(CF3)n derivatives (n = 6, 8, 10, 12, 14). The reaction with C76-D2(1) produced an abundant isomer of C2-(C76-D2(1))(CF3)10 plus smaller amounts of an isomer of C1-(C76-D2(1))(CF3)6, two isomers of C1-(C76-D2(1))(CF3)8, four isomers of C1-(C76-D2(1))(CF3)10, and one isomer of C2-(C76-D2(1))(CF3)12. The reaction with a mixture of C78-D3(1), C78-C2v(2), and C78-C2v(3) produced the previously reported isomer C1-(C78-C2v(3))(CF3)12 (characterized by X-ray crystallography in this work) and the following new compounds: C2-(C78-C2v(3))(CF3)8; C2-(C78-D3(1))(CF3)10 and Cs-(C78-C2v(2))(CF3)10 (both characterized by X-ray crystallography in this work); C2-(C78-C2v(2))(CF3)10; and C1-C78(CF3)14 (cage isomer unknown). The reaction of a mixture of soluble higher fullerenes including C84 and C90 produced the new compounds C1-C84(CF3)10 (cage isomer unknown), C1-(C84-C2(11))(CF3)12 (X-ray structure reported recently), D2-(C84-D2(22))(CF3)12, C2-(C84-D2(22))(CF3)12, C1-C84(CF3)14 (cage isomer unknown), C1-(C90-C1(32))(CF3)12, and another isomer of C1-C90(CF3)12 (cage isomer unknown). All compounds were studied by mass spectrometry, 19F NMR spectroscopy, and DFT calculations. An analysis of the addition patterns of these compounds and three other HHF(X)n compounds with bulky X groups has led to the discovery of the following addition-pattern principle for HHFs: In general, the most pyramidal cage C(sp2) atoms in the parent HHF, which form the most electron-rich and therefore the most reactive cage C−C bonds as far as 1,2-additions are concerned, are not the cage C atoms to which bulky substituents are added. Instead, ribbons of edge-sharing p-C6(X)2 hexagons, with X groups on less pyramidal cage C atoms, are formed, and the otherwise “most reactive” fullerene double bonds remain intact.