Homolytic Reactive Mass Spectrometry of Fullerenes: Peculiarities of the Reactions of C-60 with Aromatic Compounds in the Ionization Chambers of Mass Spectrometers and in Solution

作者：Lyakhovetsky Yury I^*; Shilova Elena A; Belokon Alexander I; Panz Larisa I; Tumanskii Boris L

来源：Journal of the American Society for Mass Spectrometry, 2013, 24(4): 579-588.

DOI：10.1007/s13361-012-0550-4

• C-60
• Aromatics
• Electron impact
• Homolytic reactive mass spectrometry
• Laser/desorption ionization
• Photochemical reactions

C-60 reacted with PhH, PhCl, BnH, BnNH2, and o-C2H2B10H10 in the electron impact (EI) ion source of a mass spectrometer at 300 degrees C forming phenyl, benzyl, and o-carboranyl adducts, respectively, stabilized by hydrogen addition and loss. Besides, the additions to C-60 of methyl and phenyl radicals for toluene, and a phenyl radical for benzylamine were observed. A homolytic reaction mechanism was suggested involving the reaction of the radicals formed from the aromatics under EI with C-60 at the ionization chamber walls. While the ion/molecule reaction of C-60 with benzene performed by Sun et al. under chemical ionization conditions at 200 degrees C afforded the complex C-60 center dot PhH+center dot, quite a different isomer, HC60Ph+center dot, was detected in the present study as a sequence of the different reaction mechanisms. C-60 also reacted with benzyl bromide in the laser desorption/ionization (LDI) source of a mass spectrometer to give C60CPh+. Phenyl and benzyl derivatives of C-60 were found, respectively, when the reactions of the fullerene with PhCl, BnH, and BnBr were performed in solution under ultra violet irradiation. For the reaction with toluene, the strong chemically induced dynamic electron polarization of the intermediate benzylfullerenyl radical with the reverse phase effect was found. The coincidence of the results of the mass spectrometry and solution reactions of C-60 with aromatics, even though incomplete, additionally supports the hypothesis, formulated earlier, that the former results can predict the latter ones to a significant extent and shows that this conclusion is valid for both EI and LDI initiated reactions in mass spectrometers.

• 出版日期2013-4