Journal of Solution Chemistry

, Volume 37, Issue 10, pp 1437–1448 | Cite as

Kinetic Investigation of the Electrochemical Oxidation of Bis(benzene)chromium(0) in Diethyl ketone/N,N-Dimethylformamide



The cyclic voltametric technique utilizing a platinum working electrode was applied for the investigation of the electrochemical oxidation of bis(benzene)chromium(0), (C6H6)2Cr to bis(benzene)chromium(I), (C6H6)2Cr+ in diethyl ketone (DEK), N,N-dimethylformamide (DMF), and DEK/DMF binary mixtures containing n-tetrabutylammonium hexafluorophosphate (TBAPF6) as the supporting electrolyte at T=298.15 K. The half-wave potentials (E 1/2) of the (C6H6)2Cr+/0 redox couple in DEK, DMF and DEK/DMF binary mixtures, were determined. The variation of E 1/2 with the solvent composition was found to be almost linear. The E 1/2 results were analyzed in terms of the electron-donating power of the solvent medium. The diffusion coefficients, D, were calculated using the Randles-Sevcik equation. The kinetics of the electrode reaction were investigated through the determination of the heterogeneous electron-transfer rate constants, k s, according to the electrochemical rate equation proposed by Nicholson. Furthermore, the activation Gibbs energies for the electron-transfer process (ΔG ) were also calculated. The results indicate that the redox couple (C6H6)2Cr+/0 exhibits an electrochemically reversible and diffusion-controlled process in all the investigated solvent media.


Activation Gibbs energy Electron transfer Bis(benzene)chromium(0) Cyclic voltammetry Diethyl ketone Diffusion coefficient Electron transfer rate constant Half-wave potential N,N-Dimethylformamide 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    Bunakova, L.V., Khanova, L.A., Topolev, V.V., Krishtalik, L.I.: Water-solvent liquid junction potential for some low-dielectric solvents. J. New Mat. Electrochem. Syst. 7, 241–245 (2004) Google Scholar
  2. 2.
    Gritzner, G., Kuta, J.: Recommendations on reporting electrode potentials in nonaqueous solvents. Pure Appl. Chem. 56, 461–466 (1984) CrossRefGoogle Scholar
  3. 3.
    Oshawa, Y., Aoyagui, S.: A correlation between the half-wave potential and the micelle-solubilization equilibrium of ferrocene in cationic micellar solutions. J. Electroanal. Chem. 136, 353–360 (1982) CrossRefGoogle Scholar
  4. 4.
    Bond, A.M., McLennan, E.A., Stojanovic, R.S., Thomas, F.G.: Assessment of conditions under which the oxidation of ferrocene can be used as a standard voltammetric reference process in aqueous media. Anal. Chem. 59, 2853–2860 (1987) CrossRefGoogle Scholar
  5. 5.
    Duschek, O., Gutmann, V.: Bis-biphenylchromium(I) and ferrocene as reference redox systems for comparison of half wave potentials in different solvents. Mon. Chem. 104, 990–997 (1973) CrossRefGoogle Scholar
  6. 6.
    Sharp, M., Petersson, M., Edström, K.: A comparison of the charge transfer kinetics between platinum and ferrocene in solution and in the surface attached state. J. Electroanal. Chem. 109, 271–288 (1980) CrossRefGoogle Scholar
  7. 7.
    Montenegro, M.I., Pletcher, D.: The determination of the kinetics of electron transfer using fast sweep cyclic voltammetry at microdisc electrodes. J. Electroanal. Chem. 200, 371–374 (1986) CrossRefGoogle Scholar
  8. 8.
    Pournaghi-Azar, M.H., Ojani, R.: Electrode kinetic parameters of the ferrocene oxidation at platinum, gold and glassy carbon electrodes in chloroform. Electrochim. Acta 39, 953–955 (1994) CrossRefGoogle Scholar
  9. 9.
    Saheb, A., Janata, J., Josowicz, M.: Reference electrode for ionic liquids. Electroanal. 18, 405–409 (2006) CrossRefGoogle Scholar
  10. 10.
    Gritzner, G., Gutmann, V., Schmid, R.: Oszillopolarographische Untersuchungen an Lanthanoiden in Dimethylsulfoxid und Dimethylformamid. Electrochim. Acta 13, 919–924 (1968) CrossRefGoogle Scholar
  11. 11.
    Gritzner, G.: Gibbs free energies of transfer (ΔG tr) for alkali metal ions and Tl+. Inorg. Chim. Acta 24, 5–12 (1977) CrossRefGoogle Scholar
  12. 12.
    Gritzner, G., Rechberger, P.: Polarographic and voltammetric studies in 2,2′-thiodiethanol. J. Electroanal. Chem. 109, 333–339 (1980) CrossRefGoogle Scholar
  13. 13.
    Gritzner, G., Rechberger, P., Gutmann, V.: Solvent effects on the redox potential of cis-tetracarbonyl-bis-(1,3-dimethylimidazolidin-2-ylidene) chromium(0). J. Electroanal. Chem. 114, 129–137 (1980) CrossRefGoogle Scholar
  14. 14.
    Chanfreau, S., Cognet, P., Camy, S., Condoret, J.-S.: Electrochemical determination of ferrocene diffusion coefficient in liquid media under high CO2 pressure: application to DMF-CO2 mixtures. J. Electroanal. Chem. 604, 33–40 (2007) CrossRefGoogle Scholar
  15. 15.
    Zara, A.J., Machado, S.S., Bulhões, L.O.S., Benedetti, A.V., Rabockai, T.: The electrochemistry of ferrocene in non-aqueous solvents. J. Electroanal. Chem. 221, 165–174 (1987) CrossRefGoogle Scholar
  16. 16.
    Górski, W., Galus, Z.: Solvent effects on the electrode kinetics of simple redox couples: Investigations on the electrochemical behaviour of the V(III)/V(II) system in water plus acetonitrile mixtures. J. Electroanal. Chem. 237, 209–224 (1987) CrossRefGoogle Scholar
  17. 17.
    Górski, W., Galus, Z.: Kinetics and mechanism of the V(III) + e → V(II) reaction at a mercury electrode in water plus dimethylformamide mixtures. J. Electroanal. Chem. 201, 283–299 (1986) CrossRefGoogle Scholar
  18. 18.
    Broda, J., Galus, Z.: The Mn(II)/Mn(Hg) electrode reaction in acetonitrile and its mixtures with water. J. Electroanal. Chem. 145, 147–162 (1983) CrossRefGoogle Scholar
  19. 19.
    Krishnam Raju, U.G., Venkat Rao, V., Sethuram, B., Navaneeth Rao, T.: Formal potential of the Mn(III)-Mn(II) couple in acetic acid-water mixtures at 25 °C. J. Electroanal. Chem. 133, 317–322 (1982) CrossRefGoogle Scholar
  20. 20.
    Cetnarska, M., Stroka, J.: Electrode processes of the Eu(III)/Eu(II) system in water plus hexamethylphosphortriamide mixtures. J. Electroanal. Chem. 234, 263–275 (1987) CrossRefGoogle Scholar
  21. 21.
    Geraldo, M.D., Montenegro, M.I., Pletcher, D.: The reduction of styrene at microelectrodes in toluene plus N,N-dimethylformamide mixtures. J. Electroanal. Chem. 418, 41–46 (1996) CrossRefGoogle Scholar
  22. 22.
    Matyszko, J., Scendo, M.: The stepwise reduction of Cu(II) at a platinum electrode in water plus N,N-dimethylformamide mixtures. J. Electroanal. Chem. 269, 113–128 (1989) CrossRefGoogle Scholar
  23. 23.
    Kunai, A., Toyoda, E., Kawakami, T., Ishikawa, M.: Electrochemistry of organosilicon compounds. Synthesis of poly[(1,2-dimethyldiphenyldisilanylene)phenylenes] by electrolysis of bis(chloromethylphenylsilyl)benzenes. Electrochim. Acta 39, 2089–2092 (1994) CrossRefGoogle Scholar
  24. 24.
    Fabre, B., Michelet, K., Simonet, N., Simonet, J.: Electrochemical oxidation of 1,4-dialkoxybenzenes in organic media. Reversible one-electron process in a methylene chloride/trifluoroacetic acid mixture and electropolymerization reaction in dry acetonitrile. J. Electoranal. Chem. 425, 67–75 (1997) CrossRefGoogle Scholar
  25. 25.
    Fischer, E.O., Hafner, W.: Über Aromatenkomplexe von Metallen. Zur Darstellung des Di-benzol-chroms. Z. Anorg. Allg. Chem. 286, 146–148 (1956) CrossRefGoogle Scholar
  26. 26.
    Fischer, E.O., Seeholzer, J.: Über Aromatenkomplexe von Metallen. Untersuchungen zur Di-benzol-chrom-synthese mittels Aluminium(III)-halogeniden. Z. Anorg. Allg. Chem. 312, 244–263 (1961) CrossRefGoogle Scholar
  27. 27.
    Hartl, F., Mahabiersing, T., Le Floch, P., Mathey, F., Ricard, L., Rosa, P., Záliš, S.: Electronic properties of 4,4′,5,5′-tetramethyl-2,2′-biphosphinine (tmbp) in the redox series fac-[Mn(Br)(CO)3(tmbp)], [Mn(CO)3(tmbp)]2, and [Mn(CO)3(tmbp)]: Crystallographic, spectroelectrochemical, and DFT computational study. Inorg. Chem. 42, 4442–4455 (2003) CrossRefGoogle Scholar
  28. 28.
    Hultgren, V.M., Mariotti, A.W.A., Bond, A.M., Wedd, A.G.: Reference potential calibration and voltammetry at macrodisk electrodes of metallocene derivatives in the ionic liquid [bmim][PF6]. Anal. Chem. 74, 3151–3156 (2002) CrossRefGoogle Scholar
  29. 29.
    Gosser, D.K.: Cyclic Voltammetry. VCH Publishers, New York (1993) Google Scholar
  30. 30.
    Tanaka, T., Komatsu, K.: Synthesis of the singly bonded fullerene dimer C120H2 and the difullerenylacetylene C122H2 and generation of the all-carbon dianion C1222−. J. Chem. Soc., Perkin Trans. 1, 1671–1676 (1999) CrossRefGoogle Scholar
  31. 31.
    Batterjee, S.M., Marzouk, M.I., Aazab, M.E., El-Hashash, M.A.: The electrochemistry of some ferrocene derivatives: redox potential and substituent effects. Appl. Organom. Chem. 17, 291–297 (2003) CrossRefGoogle Scholar
  32. 32.
    Ranchet, D., Tommasino, J.B., Vittori, O., Fabre, P.L.: Solvent effects on the electrochemical behavior of iron(III) Schiff base complex. J. Solution Chem. 27, 979–991 (1998) CrossRefGoogle Scholar
  33. 33.
    LeSuer, R.J., Buttolph, C., Geiger, W.E.: Comparison of the conductivity properties of the tetrabutylammonium salt of tetrakis(pentafluorophenyl)borate anion with those of traditional supporting electrolyte anions in nonaqueous solvents. Anal. Chem. 76, 6395–6401 (2004) CrossRefGoogle Scholar
  34. 34.
    He, P., Faulkner, L.R.: Intelligent, automatic compensation of solution resistance. Anal. Chem. 58, 517–523 (1986) CrossRefGoogle Scholar
  35. 35.
    Bond, A.M., Henderson, T.L.E., Mann, D.R., Mann, T.F., Thormann, W., Zoski, C.G.: A fast electron transfer rate for the oxidation of ferrocene in acetonitrile or dichloromethane at platinum disk ultramicroelectrodes. Anal. Chem. 60, 1878–1882 (1988) CrossRefGoogle Scholar
  36. 36.
    Lide, D.R.: CRC Handbook of Chemistry and Physics, 79th edn. CRC Press, Boca Raton (1998–1999) Google Scholar
  37. 37.
    Marcus, Y.: The effectivity of solvents as electron pair donors. J. Solution Chem. 13, 599–624 (1984) CrossRefGoogle Scholar
  38. 38.
    Gennett, T., Milner, D.F., Weaver, M.J.: Role of solvent reorganization dynamics in electron-transfer processes. Theory-experiment comparisons for electrochemical and homogeneous electron exchange involving metallocene redox couples. J. Phys. Chem. 89, 2787–2794 (1985) CrossRefGoogle Scholar
  39. 39.
    Connelly, N.G., Geiger, W.E.: Chemical redox agents for organometallic chemistry. Chem. Rev. 96, 877–910 (1996) CrossRefGoogle Scholar
  40. 40.
    Nicholson, R.S.: Theory and application of cyclic voltammetry for measurement of electrode reaction kinetics. Anal. Chem. 37, 1351–1355 (1965) CrossRefGoogle Scholar
  41. 41.
    Kanatharana, P., Spritzer, M.S.: Cyclic voltammetry of the iron(II)-iron(III) couple in N,N-dimethylformamide. Anal. Chem. 46, 958–959 (1974) CrossRefGoogle Scholar
  42. 42.
    Nicholson, R.S., Shain, I.: Theory of stationary electrode polarography. Single scan and cyclic methods applied to reversible, irreversible, and kinetic systems. Anal. Chem. 36, 706–723 (1964) CrossRefGoogle Scholar
  43. 43.
    Heinze, J.: Cyclic voltammetry—electrochemical spectroscopy. New analytical methods. Angew. Chem., Int. Ed. 23, 831–847 (1984) CrossRefGoogle Scholar
  44. 44.
    Weber, J., Geoffroy, M., Goursof, A., Penigault, E.: Application of the multiple scattering X. alpha. molecular orbital method to the determination of the electronic structure of metallocene compounds. Dibenzenechromium and its cation. J. Am. Chem. Soc. 100, 3995–4003 (1978) CrossRefGoogle Scholar
  45. 45.
    Robinson, R.A., Stokes, R.H.: Electrolyte Solutions, 2nd edn. Butterworths Publications, Stoneham (1959) Google Scholar
  46. 46.
    Diggle, J.W., Parker, A.J.: Solvation of ions. The ferrocene-ferricinium couple and its role in the estimation of free energies of transfer of single ions. Electrochim. Acta 18, 975–979 (1973) CrossRefGoogle Scholar
  47. 47.
    Tsierkezos, N.G.: Investigation of electron-transfer kinetics for bis(benzene) chromium(1+/0) redox couple in acetonitrile/dichloromethane binary mixtures at 298.15 K. Inorg. Chim. Acta 360, 3626–3632 (2007) CrossRefGoogle Scholar
  48. 48.
    Marcus, R.A.: Ion-ion and ion-neutral interactions in solution and measurements of dielectric constants. J. Chem. Phys. 43, 58–59 (1965) CrossRefGoogle Scholar
  49. 49.
    Marcus, R.A.: Electron transfer at electrodes and in solution: Comparison of theory and experiment. Electrochim. Acta 13, 995–1004 (1968) CrossRefGoogle Scholar
  50. 50.
    Bockris, J.O.M., Khan, S.U.M.: Quantum Electrochemistry. Plenum Press, New York (1979) Google Scholar

Copyright information

© Springer Science+Business Media, LLC 2008

Authors and Affiliations

  1. 1.Institute of Organic Chemistry and BiochemistryAcademy of Sciences of the Czech RepublicPragueCzech Republic

Personalised recommendations