Radical functionalization of [60]fullerene and its derivatives initiated by the C-center dot(CF3)(2)C6H4F radical

It was found that the 2-(p-fluorophenyl)hexafluoroisopropyl radical produce d by thermal dissociation of the Polishchuk dimer [C(CF3)(2)C6H4F](2) Can w ithdraw, under mild conditions, the H atom from the methyl group of toluene and mesitylene to form the corresponding radicals, whose addition to [60]f ullerene occurs more selectively than in the case of photochemical producti on of these radicals. Dynamics of the step-by-step multiaddition of the rad icals to C-60 was studied by ESR. It was found that the addition of benzyl radicals affords adducts containing from 3 to 5 benzyl groups, whereas no s pin-adducts with five addends were observed for more bulky 3,5-dimethylphen ylmethyl radicals. The interaction of 3,5-dimethylphenylmethyl radicals wit h the metal complexes (eta(2)-C-60)[IrH(CO)(PPh3)(2)] and (eta(2)-C-60)[Pd( PPh3)(2)] was studied for the first time. It was shown that the palladium d erivative undergoes only demetallation. In the case of the Ir complex, up t o 3 radicals add to the fullerene ligand in the same hemisphere where the t ransition metal is coordinated. The reaction rates are -5 times lower than those for C-60. The ability of 2-(p-fluorophenyl)hexafluoroisopropyl radica ls to dehydrogenate C60H36 was found.