Alkylation and phenylation of [60]- and [70]-fullerenes by the reaction with ketones in the ionization chamber of a mass spectrometer

Shilova, Elena A.; Lyakhovetsky, Yury I.; Tumanskii, B. L.; Belokon, A. I.; Nekrasov, Yurii S.

doi:10.1070/mc1999v009n05abeh001178

Cited by 14 publications

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“…In our earlier paper [10] and preliminary communication on the reaction of C 60 with ketones [1], several arguments were given in favor of the fact that the reactions of C 60 with perfluoroorganic compounds and ketone 1 in an IC occurred due to thermally and/or EI initiated homolytic dissociation of the last-named reactants to give CF 3 · and CH 3 · radicals, respectively. These radicals were supposed to react with C 60 at the IC surface, with the products undergoing ionization after vaporization.…”

Section: Resultsmentioning

confidence: 99%

“…The reactions were accompanied by hydrogen addition to products and hydrogen loss from them (Scheme 1). Mass spectra obtained in the course of experiments with C 60 and acetone (1), and acetophenone (2) performed by procedures B and A, respectively, were given in the preliminary communication [1]; those obtained with the use of methods A and B, respectively, are presented in Online Resource ( Figure S1). Two other mass spectra illustrating the Scheme are depicted in Figures 1a and b.…”

Section: Resultsmentioning

confidence: 99%

“…Figure 1 depicts mass spectra recorded during experiments with C 70 and ketones 1, and 2 (c and d, respectively). Mechanistic Studies of the Reaction Between C 60 and Acetone (1) …”

Section: Resultsmentioning

confidence: 99%

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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

Shilova

Lyakhovetsky

Belokon

et al. 2011

J. Am. Soc. Mass Spectrom.

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Our previous investigations showed that homolytic reactions of C 60 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 C 60 towards these compounds in solution or solid state. To expand the scope of this statement, C 60 and C 70 have been reacted with ketones RCOR 1 , where R and R 1 are alkyl, aryl, benzyl, and CF 3 , 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 C 60 and several ketones conducted in solution under UV irradiation have afforded Me-, Ph-, and CF 3 -derivatives of C 60 . 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.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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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

Shilova

Lyakhovetsky

Belokon

et al. 2011

J. Am. Soc. Mass Spectrom.

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“…The transfer of alkyl, aryl, and [12]carboranyl radicals from these reactants to the fullerenes was detected. Some of these processes were realized in solution under UV irradiation that indicated the above approach to be successful (25)(26)(27)(28)(29)(30).…”

Section: Introductionmentioning

confidence: 99%

Trifluoromethylation of C₆₀and C₇₀with Mercury(II) Trifluoroacetate

Lyakhovetsky

Bashilov

Tatyana

et al. 2009

Fullerenes, Nanotubes and Carbon Nanostructures

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Fullerenes C 60 and C 70 are shown to react with Hg(CF 3 COO) 2 in the ionization chamber of the electron impact source of a mass spectrometer at 300 and 310uC, yielding trifluoromethylated derivatives of the fullerenes with up to six and two CF 3 addends, respectively. For some of the products the reactions are accompanied by hydrogen addition. Based on previous mechanistic studies of the analogous reactions of C 60 with the Scherer radical (C 9 F 19 N), a mixture of perfluoronones (C 9 F 18 ), and acetone, a plausible scheme is proposed for the processes. It involves formation of the intermediate CF 3 radicals owing to electron impact or thermally initiated homolytic dissociation of the mercury(II) salt, and their further reaction with the fullerenes at the surface of the ionization chamber. Heating mixtures of the reagents under argon at 300-310uC also yields trifluoromethylated fullerenes, in agreement with the results obtained with the ionization chamber.

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“…The distinction was achieved by observing the signal of dication fullerene ions in the spectrum. The appearance of dication [60] fullerene C 60 2ϩ at m/z 360 and the absence of dication [70] fullerene C 70 2ϩ in the same spectrum indicated that the m/z 840 is indeed C 60 Me 8 ϩ . Previous experimental data on fullerene ionization has established that multiple ionization of C 60 is readily achievable by EI or collision-induced ionization [9 -12].…”

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A study on mass spectrometry of methylated [60] fullerenes using the “in-beam” electron impact technique

Al‐Matar

Badawy

2005

J. Am. Soc. Mass Spectrom.

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Mass spectra of the methylated [60]fullerenes were obtained by EI mass spectrometry using "desorption" or "in-beam" technique. The mass spectra of the methylated fullerenes, C 60 Me n , have the molecular ion peak M ϩ indicating that the product is stable under the MS (EI) conditions. The appearance of an intense peak at m/z 360 was assigned to the formation of fullerene dication C 60 ϩϩ . The remaining peaks were assigned to successive loss of methyl groups from molecular monocation and dication. A lkylation involves reaction of fullerene anions with positive alkyl groups. This leads to different addition patterns, which vary also according to the alkylation technique. These compounds are exceptionally soluble fullerenes, and promise to be useful cross-linking additives, for which the parent fullerenes are too insoluble.Their relative simplicity aids structural characterization, and many of them form suitable crystals for X-ray structure determination [1,2]. Although the small size of the methyl group and the reasonable stability of the methylfullerenes toward electron impact (EI) mass spectrometry made the reaction suitable for elucidating mechanistic features of fullerene additions, the polymethylation was a disincentive to further work [3]. The availability of high-pressure liquid chromatography (HPLC) columns dedicated to fullerene separation has enabled progress to be made.The methylated fullerenes were prepared in our previous works by different methods [1-4]: (1) reaction of fullerene with lithium followed by MeI, (2) reduction of fullerene with sodium n-propylthiolate followed by quenching with MeI, (3) reduction of fullerene by Al-Ni alloy and aqueous NaOH-dimethyl sulfoxide followed by quenching with MeI, and (4) methylation by nucleophilic substitution of halogenated fullerene C 60 Cl 6 . The resulting methylated fullerenes differ according to the method used, indicating different addition pathways: Separation of methylated fullerenes was performed with HPLC using a Cosmosil Buckyprep column with either heptane, toluene, toluene/heptane, or cyclohexane/toluene mixtures, with UV detection at 285 nm and a flow rate of 4 mL/min.Mass spectra were obtained using a VG Autospec (Sussex University, UK) mass spectrometer using 70-eV EI ionization. The samples were introduced into the mass spectrometer using the direct insertion probe with desorption CI (chemical ionization) tip operated at a temperature between 50 and 500°C. The samples were coated on a surface and inserted directly inside an ion source, as close to the ionization area as possible, by means of an extended direct insertion probe. The Љin-beamЉ technique gives a better chance of observing molecular ions in the mass spectra at the lower temperature and small sample size [5].

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Alkylation and phenylation of [60]- and [70]-fullerenes by the reaction with ketones in the ionization chamber of a mass spectrometer

Cited by 14 publications

References 2 publications

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

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

Trifluoromethylation of C₆₀and C₇₀with Mercury(II) Trifluoroacetate

A study on mass spectrometry of methylated [60] fullerenes using the “in-beam” electron impact technique

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Alkylation and phenylation of [60]- and [70]-fullerenes by the reaction with ketones in the ionization chamber of a mass spectrometer

Cited by 14 publications

References 2 publications

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

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

Trifluoromethylation of C60and C70with Mercury(II) Trifluoroacetate

A study on mass spectrometry of methylated [60] fullerenes using the “in-beam” electron impact technique

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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

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

Trifluoromethylation of C₆₀and C₇₀with Mercury(II) Trifluoroacetate