Abstract
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.
Similar content being viewed by others
References
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)
Gritzner, G., Kuta, J.: Recommendations on reporting electrode potentials in nonaqueous solvents. Pure Appl. Chem. 56, 461–466 (1984)
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)
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)
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)
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)
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)
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)
Saheb, A., Janata, J., Josowicz, M.: Reference electrode for ionic liquids. Electroanal. 18, 405–409 (2006)
Gritzner, G., Gutmann, V., Schmid, R.: Oszillopolarographische Untersuchungen an Lanthanoiden in Dimethylsulfoxid und Dimethylformamid. Electrochim. Acta 13, 919–924 (1968)
Gritzner, G.: Gibbs free energies of transfer (ΔG tr ) for alkali metal ions and Tl+. Inorg. Chim. Acta 24, 5–12 (1977)
Gritzner, G., Rechberger, P.: Polarographic and voltammetric studies in 2,2′-thiodiethanol. J. Electroanal. Chem. 109, 333–339 (1980)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
Fischer, E.O., Hafner, W.: Über Aromatenkomplexe von Metallen. Zur Darstellung des Di-benzol-chroms. Z. Anorg. Allg. Chem. 286, 146–148 (1956)
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)
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)
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)
Gosser, D.K.: Cyclic Voltammetry. VCH Publishers, New York (1993)
Tanaka, T., Komatsu, K.: Synthesis of the singly bonded fullerene dimer C120H2 and the difullerenylacetylene C122H2 and generation of the all-carbon dianion C 2−122 . J. Chem. Soc., Perkin Trans. 1, 1671–1676 (1999)
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)
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)
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)
He, P., Faulkner, L.R.: Intelligent, automatic compensation of solution resistance. Anal. Chem. 58, 517–523 (1986)
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)
Lide, D.R.: CRC Handbook of Chemistry and Physics, 79th edn. CRC Press, Boca Raton (1998–1999)
Marcus, Y.: The effectivity of solvents as electron pair donors. J. Solution Chem. 13, 599–624 (1984)
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)
Connelly, N.G., Geiger, W.E.: Chemical redox agents for organometallic chemistry. Chem. Rev. 96, 877–910 (1996)
Nicholson, R.S.: Theory and application of cyclic voltammetry for measurement of electrode reaction kinetics. Anal. Chem. 37, 1351–1355 (1965)
Kanatharana, P., Spritzer, M.S.: Cyclic voltammetry of the iron(II)-iron(III) couple in N,N-dimethylformamide. Anal. Chem. 46, 958–959 (1974)
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)
Heinze, J.: Cyclic voltammetry—electrochemical spectroscopy. New analytical methods. Angew. Chem., Int. Ed. 23, 831–847 (1984)
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)
Robinson, R.A., Stokes, R.H.: Electrolyte Solutions, 2nd edn. Butterworths Publications, Stoneham (1959)
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)
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)
Marcus, R.A.: Ion-ion and ion-neutral interactions in solution and measurements of dielectric constants. J. Chem. Phys. 43, 58–59 (1965)
Marcus, R.A.: Electron transfer at electrodes and in solution: Comparison of theory and experiment. Electrochim. Acta 13, 995–1004 (1968)
Bockris, J.O.M., Khan, S.U.M.: Quantum Electrochemistry. Plenum Press, New York (1979)
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Tsierkezos, N.G. Kinetic Investigation of the Electrochemical Oxidation of Bis(benzene)chromium(0) in Diethyl ketone/N,N-Dimethylformamide. J Solution Chem 37, 1437–1448 (2008). https://doi.org/10.1007/s10953-008-9315-x
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10953-008-9315-x