Homolytic Reactive Mass Spectrometry of Fullerenes: Interaction of C60 and C70 with Ketones in the Electron Impact Ion Source of a Mass Spectrometer and the Comparison of Results with Those of Photochemical Reactions of C60 with Several Ketones in Solution

Our previous investigations showed that homolytic reactions of C60 with a number of perfluoroorganic and organomercury(II) compounds occurring under electron impact (EI) in the ionization chamber (IC) of a mass spectrometer could predict the reactivity of C60 towards these compounds in solution or solid state. To expand the scope of this statement, C60 and C70 have been reacted with ketones RCOR1, where R and R1 are alkyl, aryl, benzyl, and CF3, in an IC under EI to yield products of the addition of R· and R 1 · radicals to the fullerenes, paramagnetic ones being stabilized by hydrogen addition and loss. Experimental evidence in support of a mechanism involving homolytic dissociation of ketone molecules via superexcited states to afford these radicals that react with the fullerenes at the IC surface has been obtained. As anticipated, the reactions between C60 and several ketones conducted in solution under UV irradiation have afforded Me-, Ph-, and CF3-derivatives of C60. However, some other products have been identified by mass spectrometry and their formation is reasonably explained. When decalin has been employed as a solvent, decalinyl derivatives of the fullerene have been found among the products and the (9-decalinyl)fullerenyl radical has been registered by EPR. Thus, incomplete but reasonable conformity of the results of the reactions of fullerenes with ketones in an IC under EI with those of the reactions of the same reagents in solution under UV irradiation has been demonstrated, and the former results can predict the latter ones to a reasonable extent.