Thermodynamic and kinetic characteristics of intermediates of electrode reactions: A comparative investigation of a number of alkylaryl and alkyl halide radicals by the laser photoemission methods
作者： A. G. Krivenko , A. S. Kotkin , V. A. Kurmaz
DOI: 10.1007/S11175-005-0025-Z
关键词: Reaction rate constant 、 Photochemistry 、 Chemistry 、 Trifluoromethyl 、 Halide 、 Redox 、 Electron transfer 、 Tafel equation 、 Alkyl 、 Physical chemistry 、 Radical
摘要: A comparative investigation of thermodynamic and kinetic properties a number alkylaryl intermediates (benzyl benzhydryl radicals) alkyl halide (chloromethyl, dichloromethyl, trifluoromethyl is performed by methods laser photoemission. Techniques, aimed at the determination (standard potentials E 0 redox pairs R⋅/R-, standard adsorption free energies -ΔG a(R) 0 , values rate constants W 0 an equilibrium potential, as well lifetimes (times death in bulk) τR radicals R⋅ τX products their reduction R-) from comparison Tafel plots for quasi-reversible with calculated ones E 0—from irreversible electroreduction intermediates, are presented. The transition to aprotic solvents E∼E 0 observed only case benzyl, benzhydryl, radicals, which this particular collection obtained, not chloromethyl dichloromethyl radicals. In characteristics (E 0, W 0) estimated absolute rates electroreduction. Possible reasons differences probability reversible electron transfer discussed systems studied.
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sci-hub.se 参考文章(56)
George V. Buxton, Clive L. Greenstock, W. Phillips Helman, Alberta B. Ross, Critical Review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (⋅OH/⋅O− in Aqueous Solution Journal of Physical and Chemical Reference Data. ,vol. 17, pp. 513- 886 ,(1988) , 10.1063/1.555805
Marek Lieder, Calculation of the Standard Potentials of the Dithiocarbamate/thiuram Disulfide Redox System via Thermochemical Cycles and Computational Electrochemistry Phosphorus Sulfur and Silicon and The Related Elements. ,vol. 178, pp. 179- 189 ,(2003) , 10.1080/10426500307784
Christian Amatore, Catherine Combellas, Jean Pinson, Mehmet A. Oturan, Sabine Robvieille, Jean Michel Saveant, Andre Thiebault, Electrochemically induced SRN1 aromatic nucleophilic substitution. Absolute reactivities of phenyl derivatives in liquid ammonia Journal of the American Chemical Society. ,vol. 107, pp. 4846- 4853 ,(1985) , 10.1021/JA00303A007
Valery V. Konovalov, Yury D. Tsvetkov, Isaak I. Bilkis, Sergey S. Laev, Vitaly D. Shteingarts, The decay rates of radical anions of polyfluorobenzoic acids in water Mendeleev Communications. ,vol. 3, pp. 51- 53 ,(1993) , 10.1070/MC1993V003N02ABEH000218
Juan Bertran, Iluminada Gallardo, Miquel Moreno, Jean Michel Saveant, Dissociative electron transfer. Ab initio study of the carbon-halogen bond reductive cleavage in methyl and perfluoromethyl halides. Role of the solvent Journal of the American Chemical Society. ,vol. 114, pp. 9576- 9583 ,(1992) , 10.1021/JA00050A042
C. Fontanesi, P. Baraldi, M. Marcaccio, On the dissociation dynamics of the benzyl chloride radical anion. An ab initio dynamic reaction coordinate analysis study Journal of Molecular Structure-theochem. ,vol. 548, pp. 13- 20 ,(2001) , 10.1016/S0166-1280(00)00863-0
José Gonzalez, Philippe Hapiot, Valery Konovalov, Jean-Michel Savéant, None, Investigating the reduction characteristics of transient free radicals by laser-pulse electron photo-injection mechanism diagnostic criteria and determination of reactivity parameters from time-resolved experiments Journal of Electroanalytical Chemistry. ,vol. 463, pp. 157- 189 ,(1999) , 10.1016/S0022-0728(98)00435-5
Viktor A Benderskii, Alexander G Krivenko, The electrochemistry of short-lived intermediate species Russian Chemical Reviews. ,vol. 59, pp. 1- 22 ,(1990) , 10.1070/RC1990V059N01ABEH003506
Kurt V. Mikkelsen, Steen U. Pedersen, Henning Lund, Peter Swanstroem, A new and rigorous method for calculating intramolecular reorganization energies for electron-transfer reactions: applied for self-exchange reactions involving alkyl and benzyl radicals The Journal of Physical Chemistry. ,vol. 95, pp. 8892- 8899 ,(1991) , 10.1021/J100175A087
Alexander G. Krivenko, Alexander S. Kotkin, Vladimir A. Kurmaz, The β-hydroxyethyl radical as a model system for two-pathway electroreduction in the presence of proton donors Mendeleev Communications. ,vol. 8, pp. 56- 58 ,(1998) , 10.1070/MC1998V008N02ABEH000922