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Mechanism of the reaction of 1,1 -diethylferrocene and decamethylferrocene with peroxides in organic solvents.(Report)

Fomin, V. M. ; Terekhina, A. A. ; Zaitseva, K. S.

Russian Journal of General Chemistry, Dec, 2013, Vol.83(12), p.2324(7) [Periódico revisado por pares]

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  • Título:
    Mechanism of the reaction of 1,1 -diethylferrocene and decamethylferrocene with peroxides in organic solvents.(Report)
  • Autor: Fomin, V. M. ; Terekhina, A. A. ; Zaitseva, K. S.
  • Assuntos: Biphenyl (Compound) ; Metallocenes ; Chromophores ; Peroxides ; Pyridine ; Iron Compounds
  • É parte de: Russian Journal of General Chemistry, Dec, 2013, Vol.83(12), p.2324(7)
  • Descrição: Byline: V. M. Fomin (1), A. A. Terekhina (1), K. S. Zaitseva (1) Abstract: Kinetic relationships of oxidation of 1,1 -diethylferrocene and decamethylferrocene with peroxides ROOR (R = H, t-[C.sub.4]H.sub.9) in organic solvents were studied and the composition of oxidation products was established. It is shown that reactivity of ([C.sub.5][H.sub.4][C.sub.2]H.sub.[5).sub.2]Fe is significantly lower than that of C[p*.sub.2]Fe [Cp* = I*.sup.5-C.sub.5(CH.sub.3).sub.5] which is seen from the ability of the first metal complex to undergo oxidation with a notable rate only in the presence of Bronsted acids, whereas the second substance is oxidized both in the presence and in the absence of these acids. Two possible mechanisms of oxidation of metal complexes in the presence of strong acids are discussed. One of them is based on the ability of ferrocene to fast and equilibrium protonation with the formation of [Cp.sub.2]Fe.sup.+--H structure. Another one considers the ability of metal complexes to coordinate peroxides with the formation of weakly bound charge transfer complexes of the composition [Cp.sub.2]Fe.sup.[delta]+*ROOR.sup.[delta]-. The possibility of their formation is confirmed by the oxidation of [Cp.sub.2]Fe with hydroperoxides in the absence of acids. Author Affiliation: (1) Lobachevskii Nizhni Novgorod State University, pr. Gagarina 23, Nizhni Novgorod, 603950, Russia Article History: Registration Date: 28/01/2013 Received Date: 14/01/2013 Online Date: 31/01/2014 Article note: Original Russian Text (c) V.M. Fomin, A.A. Terekhina, K.S. Zaitseva, 2013, published in Zhurnal Obshchei Khimii, 2013, Vol. 83, No. 12, pp. 2041--2047.
  • Idioma: English

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