Abstract
The oxidation of Fc(C2H5)2, Fc(COCH3)2, and Fc(PPh2)2, where Fc is a ferrocene, with hydrogen peroxide in aprotic (dioxane and acetonitrile) and hydroxyl-containing (ethanol, acetonitrile–water, and water) solvents is studied via electron spectroscopy. The reactivity of these metal complexes relative to an oxidant is due to the electron-donor or electron-acceptor properties of substituents, their sizes, and their capability for the specific solvation by a particular solvent. Possible mechanisms of the oxidation of metal complexes are discussed. When Fc(PPh2)2 is oxidized, the formation of ferrocenyl cation Fc+(PPh2)2 is due to the redox isomerism of ferrocenylphosphonium cation Fc(PPh2)P+Ph2, which can form during the reaction between protonated complex Fc(PPh2)P(H+)Ph2 and H2O2.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
V. M. Fomin, A. A. Terekhina, and K. S. Zaitseva, Russ. J. Gen. Chem. 83, 2324 (2013).
M. G. Ikonomou, J. Sunner, and P. Kerrable, J. Phys. Chem. 92, 6308 (1988).
Meot-Ner (Mautner), J. Am. Chem. Soc. 111, 2830 (1989).
Yu. A. Borisov and N. A. Ustynyuk, Russ. Chem. Bull. 51, 1900 (2002).
J. W. Lauher and R. Hoffman, J. Am. Chem. Soc. 98, 1729 (1976).
M. L. H. Green, Organometallic Compounds: The Transition Elements (Methuen, London, 1968).
A. N. Egorochkin, M. G. Voronkov, and O. V. Kuznetsova, Polarization Effect in Organic, Organoelement, and Coordination Chemistry (Nizh. Novgorod, 2008), p. 61 [in Russian].
C. Hansch, A. Leo, and R. W. Taft, Chem. Rev. 91, 165 (1991).
Organic Solvents. Physical Properties and Methods of Purification, Ed. by A. Weisberger (Interscience, New York, 1955).
V. M. Fomin, E. A. Orlova, and K. S. Zaitseva, Russ. J. Gen. Chem. 84, 722 (2014).
O. N. Temkin, Homogeneous Catalysis by Metal Complexes: Kinetic Aspects and Mechanisms (Akademkniga, Moscow, 2008; Wiley, Chichester, 2012), p. 833.
E. M. Arnett, in Progress in Physical Organic Chemistry, Ed. by S. G. Cohen, A. Streutweiser, and R. W. Taft (Wiley, New York, 1963), Vol. 1, p. 223.
E. P. Hunter and S. G. Lias, J. Phys. Chem. Ref. Data 27, 413 (1998).
Methods of Organoelement Chemistry. Organoiron Compounds, Ed. by A. N. Nesmeyanov and K. A. Kochetkov (Nauka, Moscow, 1983) [in Russian].
K. L. Rinehart, Jr., C. J. Michejda, and P. A. Kittle, J. Am. Chem. Soc. 81, 2162 (1959).
V. Weinmayr, J. Am. Chem. Soc. 77, 3009 (1955).
V. M. Fomin, K. S. Zaitseva, M. N. Sharova, and M. N. Klimova, Russ. J. Gen. Chem. 86, 1077 (2016).
J. L. Robbins, N. Edelstein, B. Spenser, and J. C. Smart, J. Am. Chem. Soc. 104, 1882 (1982).
Author information
Authors and Affiliations
Corresponding author
Additional information
Original Russian Text © V.M. Fomin, K.S. Kochetkova, M.S. Galkina, 2017, published in Zhurnal Fizicheskoi Khimii, 2017, Vol. 91, No. 7, pp. 1186–1192.
Rights and permissions
About this article
Cite this article
Fomin, V.M., Kochetkova, K.S. & Galkina, M.S. Effect of solvent, electronic, and steric factors on the reactivity of 1,1'-diethylferrocene, 1,1'-diacetylferrocene, and 1,1'-bis(diphenylphosphino)ferrocene towards hydrogen peroxide. Russ. J. Phys. Chem. 91, 1285–1291 (2017). https://doi.org/10.1134/S0036024417070111
Received:
Published:
Issue Date:
DOI: https://doi.org/10.1134/S0036024417070111