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Electrochemical approach to direct homogeneous chemical cyanation of ferricenium salts: The complexing of system components

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Abstract

An unusual homogeneous chemical reaction of a direct cyanation of ferricenium salts by hydrocyanic acid is analyzed on the basis of an electrochemical approach and the notions of the chemistry of coordination compounds about an inner-sphere electron transfer. The complexing between a ferricenium cation and cyanide anion is confirmed experimentally using a potentiometric titration of aqueous solutions of ferricenium tetrafluoroborate by hydrocyanic acid. Variations of the mechanism of a rebound substitution of the CN group in the cyclopentadienyl ring for the hydrogen atom are considered. The mechanism is based on the notion about an inner-sphere redox reaction between the Fe(III) atom of a ferricenium cation and the CN- anion. The magnitude and sign of the difference between standard potentials of systems [(C5H5)2M)]+/(C5H5)2M and CN+/CN- are found to represent a thermodynamic criterion indicating whether cations of metallocenes [(C5H5)2M]+ may be directly cyanated by hydrocyanic acid.

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References

  1. Kealy, T.J. and Pauson, P.L.,Nature (London), 1951, vol. 168, p. 1039.

    Article  CAS  Google Scholar 

  2. Miller, S.A., Tebboth, J.A., and Tremaine, J.F.,J. Chem. Soc., 1952, p. 632.

  3. Wilkinson, G., Rosenblum, M., Whiting, M.C., and Woodward, R.B.,J. Am. Chem. Soc., 1952, vol. 74, p. 2125.

    Article  CAS  Google Scholar 

  4. Perevalova, E.G., Reshetova, M.D., and Grandberg, K.I.,Metody elementoorganicheskoi khimii: Zhelezoorganicheskie soedineniya: Ferrotsen (Methods of the Elementorganic Chemistry: Organoiron Compounds: Ferrocene), Moscow: Nauka, 1983.

    Google Scholar 

  5. Nesmeyanov, A.N.,Khimiya ferrotsena (The Ferrocene Chemistry), Moscow: Nauka, 1969.

    Google Scholar 

  6. Nesmeyanov, A.N.,Ferrotsen i rodstvennye soedineniya (Ferrocene and Related Compounds), Moscow: Nauka, 1982.

    Google Scholar 

  7. Kravtsov, V.I.,Ravnovesie i kinetika elektrodnykh reaktsii kompleksov metallov (The Equilibrium and Kinetics of Electrode Reactions Involving Metal Complexes), Leningrad: Khimiya, 1985.

    Google Scholar 

  8. Cotton, F.A. and Wilkinson, G.,Advanced Inorganic Chemistry: A Comprehensive Text, New York: Wiley Interscience, 1966.

    Google Scholar 

  9. Nesmejanow, A.N., Perewalowa, E.G., and Jurjewa, L.P.,Chem. Ber., 1960, vol. 93, p. 2729.

    Article  Google Scholar 

  10. Perevalova, E.G., Yur’eva, L.P., and Baukov, Yu.I.,Dokl. Akad. Nauk SSSR, 1960, vol. 135, p. 1402.

    CAS  Google Scholar 

  11. Nesmeyanov, A.N., Lubovich, A.A., Yur’eva, L.P.,et al., Izv. Akad. Nauk SSSR, Ser. Khim., 1967, p. 935.

  12. Nesmeyanov, A.N., Perevalova, E.G., and Yur’eva, L.P.,Izv. Akad. Nauk SSSR, Ser. Khim., 1968, p. 2406.

  13. Bunnet, J.F. and Zahler, R.E.,Chem. Rev., 1951, vol. 49, p. 273.

    Article  Google Scholar 

  14. Bunnet, J.F.,Quart. Rev., 1958, vol. 12, p. 1.

    Article  Google Scholar 

  15. Sauer, J. and Huisgen, R.,Angew. Chem., 1960, vol. 72, p. 294.

    Article  CAS  Google Scholar 

  16. Nesmeyanov, A.N., Perevalova, E.G., Yur’eva, L.P., and Kakurina, L.N.,Izv. Akad. Nauk SSSR, Ser. Khim., 1964, p. 1897.

  17. Pendin, A.A., Leont’evskaya, P.K., and Bundina, T.K.,Kinet. Katal., 1977, vol. 18, no. 5, p. 1325.

    CAS  Google Scholar 

  18. Nesmeyanov, A.N., Perevalova, E.G., Yur’eva, L.P., and Grandberg, K.I.,Izv. Akad. Nauk SSSR, Ser. Khim., 1962, p. 1772.

  19. Nesmeyanov, A.N., Perevalova, E.G., and Grandberg, K.I.,Izv. Akad. Nauk SSSR, Ser. Khim., 1964, p. 1903.

  20. Nesmeyanov, A.N., Yur’eva, L.P., and Perevalova, E.G.,Izv. Akad. Nauk SSSR, Ser. Khim., 1967, p. 578.

  21. Khimicheskaya entsiklopediya (Encyclopedia of Chemistry), Moscow: Sovetskaya Entsyklopediya, 1988, vol. 1, p. 428.

  22. Khimiya psevdogalogenidov (The Chemistry of Pseudohalides), Golub, M.A., Keler, Kh., and Skopenko, V.V., Eds., Kiev: Vishcha Shkola, 1981.

    Google Scholar 

  23. Burger, K.,Solvation, Ionic and Complex Formation Reactions in Nonaqueous Solvents: Experimental Methods for Their Investigation, Amsterdam: Elsevier, 1983.

    Google Scholar 

  24. Page, J.F. and Wilkinson, J.,J. Am. Chem. Soc., 1952, vol. 74, p. 6149.

    Article  CAS  Google Scholar 

  25. Latimer, W.,The Oxidation States of the Elements and Their Potentials in Aqueous Solutions, New York: Prentice-Hall, 1952.

    Google Scholar 

  26. Nonhebel, D.C., Tedder, J.M., and Walton, J.C.,Radicals, Cambridge: Cambridge Univ. Press, 1979.

    Google Scholar 

  27. Reutov, O.A. and Brusova, G.P.,Svobodnoradikal’nye zameshcheniya u nasyshchennogo atoma ugleroda (Free-Radical Substituents at a Saturated Carbon Atom), Moscow: Mosk. Gos. Univ., 1988.

    Google Scholar 

  28. Koyama, K., Susuki, T., and Tsutsumi, Sh.,Tetrahedron Lett., 1965, p. 627.

  29. Nefedov, V.A. and Tarygina, L.K.,Zh. Org. Khim., 1976, vol. 12, p. 2012.

    CAS  Google Scholar 

  30. Broadhead, G.D., Osgerby, J.M., and Pauson, P.L.,J. Chem. Soc., 1958, p. 650.

  31. Metody elementoorganicheskoi khimii: Kobal’t, nikel’, platinovye metally (Methods of the Elementoorganic Chemistry: Cobalt, Nickel, and Platinum Metals), Nesmeyanov, A.N. and Kocheshkov, K.A., Eds., Moscow: Nauka, 1978, pp. 192, 306.

    Google Scholar 

  32. Nikol’skii, B.P., Pendin, A.A., and Zakhar’evskaya, M.S.,Dokl. Akad. Nauk SSSR, 1965, vol. 160, p. 1131.

    CAS  Google Scholar 

  33. Fridman, Ya.D.,Zh. Neorg. Khim., 1958, vol. 3, p. 1865.

    CAS  Google Scholar 

  34. Koepp, H.-M., Wendt, H., and Strehlow, H.,Z Electrochem., 1960, vol. 64, p. 483.

    CAS  Google Scholar 

  35. Bond, A., Casey, A., and Theckeray, J.,J. Chem. Soc., Dalton Trans., 1974, p. 773.

  36. Tomilov, A.P., Chernykh, I.N., and Kargin, Yu.M.,Elektrokhimiya elementoorganicheskikh soedinenii: elementy I, II, i III grupp periodicheskoi sistemy i perekhodnye metally (The Electrochemistry of Organometallic Compounds: Elements of Groups I, II, and III of the Periodic Table and the Transition Metals), Moscow: Nauka, 1985, p. 100.

    Google Scholar 

  37. Wilson, R., Warren, L., and Hawthorne, M.,J. Am. Chem. Soc., 1969, vol. 91, p. 758.

    Article  CAS  Google Scholar 

  38. Gubin, S.P. and Perevalova, E.G.,Dokl. Akad. Nauk SSSR, 1962, vol. 143, p. 1351.

    CAS  Google Scholar 

  39. Karyakin, Yu.V. and Angelov, I.I.,Chistye khimicheskie reaktivy (Pure Chemical Reagents), Moscow: Goskhimizdat, 1955.

    Google Scholar 

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  1. Moscow State University, Vorob’evy gory, 119899, Moscow, Russia

    L. N. Nekrasov & L. P. Yur’eva

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  1. L. N. Nekrasov
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  2. L. P. Yur’eva
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Dedicated to the memory of Academician A.N. Nesmeyanov, in connection with his centennial.

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Nekrasov, L.N., Yur’eva, L.P. Electrochemical approach to direct homogeneous chemical cyanation of ferricenium salts: The complexing of system components. Russ J Electrochem 36, 299–307 (2000). https://doi.org/10.1007/BF02827974

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  • DOI: https://doi.org/10.1007/BF02827974

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