Fast Techniques in Electrochemistry Application to the Study of Chemical Reactivity
Electron transfers and the reactions they initiate have received a considerable attention in the recent years both in the organic and organometallic fields1 Indeed it has been recently recognized that a number of so-thought elementary reactions may involve — or — may be triggered by — single electron transfers. The spreading of these new concepts coincided with the development of new experimental and conceptual tools in electrochemistry. Indeed up to the middle of the seventies most of electrochemical studies were related to the delineation of the basic and elementary chemical acts associated with electron transfers2. The method was then mostly limited to problems involving a single reactive path occuring within time scales larger than a few milliseconds. Yet the basic concepts thus developped have allowed, in the past decade, the extension of the electrochemical approaches to situations which interest and complexity make them particularly adequate to investigate a variety of essential problems in chemical reactivity. Concomitantly the time scale window of the method has been enlarged to the sub-nanosecond region. This together with the inherent simplicity -and low cost aspects — of the technique explain its recent diffusion and adoption by many research groups in the fields of organic or organometallic chemical reactivity.
KeywordsElectron Transfer Chemical Reactivity Reduction Wave Single Electron Transfer Capacitive Current
Unable to display preview. Download preview PDF.
- 1.See e.g. (a): J.K. Kochi, J. Organomet. Chem., 300 (1986) 139., and (b): M. Chanon, Bull. Soc. Chim. Fr., (1985) 209, and references therein.Google Scholar
- 2.See e.g. A.J. Bard and L.R. Faulkner, in “Electrochemical Methods”, Wiley, New-York, 1980.Google Scholar
- 3.C.P. Andrieux and J.M. Savéant, “Electrochemical Reactions”, in “Investigation of Rates and Mechanism of Reactions”, Vol.6, 4/E, Part 2, C.F. Bernasconi, Ed., Wiley, New-York, 1986 ; pp. 305–390.Google Scholar
- 4.P. Delahay, in “Double Layer and Electrode Kinetics”, Wiley, New-York, 1965.Google Scholar
- 5.(a) J.M. Savéant, J. Electroanal. Chem., 112 (1980) 175 ; (b) 143 (1983) 447 ; (c) C. Amatore, unpublished results.Google Scholar
- 7.Adapted from an original presentation by P.T. Kissinger, in “Laboratory Techniques in Electroanalytical Chemistry”, P.T. Kissinger and W.R. Heineman, Eds., M. Dekker, New-York, 1984 ; p.6.Google Scholar
- 11.C. Fabre, R. Fugnitto, H. Strzelecka, C.R. Acad. Sc., ser. C, 282 (1976) 175.Google Scholar
- 14.See e.g. C. Amatore, J. Chaussard, J. Pinson, J.M. Savéant and A. Thiébault, J. Am. Chem. Soc., 101 (1079) 6012, and refs. therein.Google Scholar
- 16.J.M. Savéant, J. Am. Chem. Soc., in press.Google Scholar
- 17.See e.g. C. Amatore, M. Gareil, M.A. Oturan, J. Pinson, J.M. Savéant and A. Thiébault, J. Am. Chem. Soc.,107 (1985) 3451.Google Scholar
- 18.C. Amatore, M.R. Deakin and R.M. Wightman, J. Electroanal. Chem., in press.Google Scholar
- 20.C. Amatore, C. Combellas, F. Pflüger and A. Thiébault, unpublished results (1987).Google Scholar