Abstract
Specific features of formyl- and acetylferrocene oxidation with peroxides ROOR (R = H, tert-C4H9) in different solvents are studied. It is shown that despite of the presence in complexes of strong electronacceptor substituents they can be oxidized with hydrogen peroxide in the absence of strong Brønsted acids. Dilution of water with organic solvent leads to deceleration and complete standstill of the reaction. In the absence of acids the second order of the process with respect to peroxide and first one with respect to the metal complex was evaluated. In the presence of perchloric or trifluoroacetic acid the order with respect to peroxide decreases to the first one. The dependence of the reaction rate on the concentration of acid has an extremum point. The activity of other peroxides in the reaction with the above-mentioned compounds is significantly lower than the activity of hydrogen peroxide. Probable alternative mechanisms of oxidation of the abovementioned ferrocenes with hydrogen peroxide in the presence and in the absence of acids differing in the way of coordination of reagents with one another and considering direct participation of substituent in the oxidation is suggested.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Fomin, V.M. and Shirokov, A.E., Russ. J. Gen. Chem., 2012, vol. 82, no. 6, p. 1080.
Egorochkin, A.N., Voronkov, M.G., and Kuznetsova, O.V., Polyarizatsionnyi effekt v organicheskoi, elemento-organicheskoi i koordinatsionnoi khimii (Polarization Effects in the Organic, Ogranoelement, and Coordination Chemistry), Nizhnii Novgorod, Nizhnii Novgorod. Gos. Univ., 2008, p. 61.
Mathieu, J. and Poniko, P., Kurs teoreticheskikh osnov organicheskoi khimii (Course of Theoretical Principles in Organic Chemistry), Moscow: Mir, 1975, p. 530.
Sykes, P., A Guidebook to Mechanism in Organic Chemistry, Dunod, 1966. Translated under the title Mekhanizmy reaktsii v organicheskoi khimii, Moscow: Khimiya, 1973, p. 198.
Metody elementoorganicheskoi khimii. Zhelezoorganicheskie soedineniya (Methods in Organoelement Chemistry. Organoiron Compounds), Nesmeyanov, A.N. and Kochetkov, K.A., Moscow: Nauka, 1984, p. 35.
Berezin, I.V. and Martinek, K., Osnovy fizicheskoi khimii i fermentativnogo kataliza (Essential Physical Chemistry and Fermentative Catalysis), Moscow: Vysshaya Shkola, 1977, p. 53.
Energii razryva khimicheskikh svyazei. Potenstialy ionizatsii i srodstvo k elektronu (Energies of Cleavage of Chemical Bonds. Ionization Potentials and Electron Affinity), Kondrat’ev, V.N., Ed., Moscow: Nauka, 1974, p. 106.
Fomin, V.M., Kolmakov, A.O., and Aleksandrov, Yu.A., Koord. Khim., 1988, vol. 14, no. 6, p. 777.
Fomin, V.M. and Shirokov, A.E., Russ. J. Gen. Chem., 2009, vol. 79, no. 11, p. 2304.
Comprehensive Organic Chemistry, vol. 1, Oxygen Compounds, Stoddart, J.F., Ed., Oxford: Pergamon Press, 1979.
Day, M.C and Selbin, J., Theoretical Inorganic Chemistry, Reinhold Book Corp., 1969. Translated under the title Teoreticheskaya neorganicheskaya khimiya, Moscow: Khimiya, 1976, p. 330.
Bell, R.P., The Proton in Chemistry, Cornell University Press, 1973. Translated under the title Proton v khimii, Moscow: Mir, 1977, p. 155.
Author information
Authors and Affiliations
Corresponding author
Additional information
Original Russian Text © V.M. Fomin, E.A. Orlova, K.S. Zaitseva, 2014, published in Zhurnal Obshchei Khimii, 2014, Vol. 84, No. 4, pp. 645–655.
Rights and permissions
About this article
Cite this article
Fomin, V.M., Orlova, E.A. & Zaitseva, K.S. Specific features of formyl- and acetylferrocene oxidation with peroxides in water and organic solvents. Russ J Gen Chem 84, 722–732 (2014). https://doi.org/10.1134/S1070363214040215
Received:
Published:
Issue Date:
DOI: https://doi.org/10.1134/S1070363214040215