The reactivity of ferrocenylalkyl azoles under the conditions of electrospray ionization

Nekrasov, Y.S.; Borisov, Y.A.; Skazov, R.S.; Simenel, A.A.; Snegur, L.V.; Belousov, Y.A.; Rodionov, A.N.

Авторы: Nekrasov Yu S., Borisov Yu A., Skazov R.S., Simenel A.A., Snegur L.V., Belousov Yu A., Rodionov A.N.
Журнал: Journal of Organometallic Chemistry
Том: 694
Номер: 12
Год издания: 2009
Издательство: Elsevier BV
Местоположение издательства: Netherlands
Первая страница: 1807
Последняя страница: 1812
Аннотация: Under the conditions of electrospray ionization of ferrocenylalkyl azoles FcCH(R)X R – H, Me, XH – 2-methyl imidazole, pirazole the processes of oxidation, protonation, fragmentation and ferrocenylalkylation to form, molecular ions [M]+, protonated molecules [M+H]+, ferrocenylalkyl cations [FcCHR]+ and bisferrocenylalkyl azole cations [(FcCHR)2X]+, respectively, take place. Using special experimental techniques (deuterated solvents, saturation of ionic source of an ESI mass-spectrometer by the vapors of solvents, the experiments under the ‘‘inverse” ESI conditions when the solvent is subjected to electrospray in the presence of ferrocenylalkyl derivative vapours) and quantum-chemical calculations at the level of the B3LYP/LanL2DZ theory the scheme of the formation of these ions in a gas phase according to the mechanism of ‘‘activating protonation” was suggested. it was found that all these ions are formed through the protonation stage, which is taking place mainly in a gas phase. The key stage is the exothermic process of the protonation of the initial compounds by hydroxonium ions giving rise to protonated [M+H]+ molecules which further oxidize and alkylate ferrocenylalkylazoles to form molecular radical cations and bisferrocenylalkyl azole ions [FcCH(Me)-X-CH(Me)Fc]+. The decomposition of protonated ions with the elimination of the azole molecule gives rise to ferrocenylalkyl cations [FcCHR]+ capable in turn of oxidizing and alkylating the initial compounds.
Добавил в систему: Сименел Александр Александрович

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