A model for pathways of radical addition to fullerenes

Synthesis and Structures of Fullerene Bromides and Chlorides

“…Alternatively, the reaction may proceed through a radical mechanism involving the addition of Br · with subsequent Br/Cl exchange. It was assumed that addition to C 70 X 10 occurs at sites of maximum free valence in closed-shell molecules and of maximum spin density in the radicals (as also assumed earlier [42] to account for the formation of C 60 X 6 and C 70 X 10 isomers in the radical addition of bulky groups to C 60 and C 70 ). It was found that the location of the most reactive site in C 70 X 10 (X = Br or Cl) near the one pole of the molecule should finally result in the structures of the C 70 Cl 16 shown in Figure 8, b.…”

High‐Temperature Synthesis of the Surprisingly Stable C1‐C70(CF3)10 Isomer with a para7–meta–para Ribbon of Nine C6(CF3)2 Edge‐Sharing Hexagons

“…[8][9][10] The exception is the recently described compound C 70 (tBuOO) 10 , which has the C 2 structure also shown in Figure 1 with an all-para ribbon of nine edge-sharing C 6 (tBuOO) 2 hexagons (p 9 ), presumably because the tBuOO groups are too large to be on adjacent cage C atoms. [11] We recently reported the synthesis of batches (more than 10 mg) of a single isomer of C 70 (CF 3 ) 10 at 470 8C in 27% overall yield based on converted C 70 .…”

Structures and Electronic Properties of C56Cl8 and C56Cl10 Fullerene Compounds

“…The relative energies of the 25 C 56 Cl 10 isomers considered herein are predicted at the B3LYP/3-21G level and are listed in Table 2. Obviously, C 56 Cl 10 Fowler and co-worker provided a model for the pathways of radical addition to fullerenes [35] based on Hückel's molecular orbital (HMO) theory. One can add a radical to the site of highest free-valence index and subsequently add a second radical to the site with the highest spin density.…”