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Mechanism of the reaction of 1,1′-diethylferrocene and decamethylferrocene with peroxides in organic solvents

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

Russian Journal of General Chemistry, 2013, Vol.83(12), pp.2324-2330 [Periódico revisado por pares]

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Título:
Mechanism of the reaction of 1,1′-diethylferrocene and decamethylferrocene with peroxides in organic solvents
Autor: Fomin, V. ; Terekhina, A. ; Zaitseva, K.
É parte de: Russian Journal of General Chemistry, 2013, Vol.83(12), pp.2324-2330
Descrição: Kinetic relationships of oxidation of 1,1′-diethylferrocene and decamethylferrocene with peroxides ROOR (R = H, t -C 4 H 9 ) in organic solvents were studied and the composition of oxidation products was established. It is shown that reactivity of (C 5 H 4 C 2 H 5 ) 2 Fe is significantly lower than that of Cp* 2 Fe [Cp* = η 5 -C 5 (CH 3 ) 5 ] which is seen from the ability of the first metal complex to undergo oxidation with a notable rate only in the presence of Brønsted 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 2 Fe + —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 2 Fe δ+ ·ROOR δ- . The possibility of their formation is confirmed by the oxidation of Cp 2 Fe with hydroperoxides in the absence of acids.
Idioma: Inglês

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