Thermodynamic and kinetic characteristics of one-electron transfer reactions in N-alkylaniline-tetracyanoethylene charge transfer complex systems |
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Authors: | V S Kuts A M Golubenkova V D Pokhodenko |
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Institution: | (1) L. V. Pisarzhevskii Institute of Physical Chemistry, Academy of Sciences of the Ukrainian SSR, Kiev |
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Abstract: | One-electron transfer reactions in systems containing an N,N-dialkylaniline (D) and tetracyanoethylene (A) in methylene chloride proceed through the formation of AD and AD2 charge transfer complexes. The tetracyanoethylene -system and nitrogen unshared electron pair of the N,N-dialkylaniline participate in the formation of the charge transfer complex. The equilibrium constants for complex formation K and rates of formation of the TCE– radical-anions k were determined for this reaction. The sign of the regression coefficient in the correlation between the thermodynamic (K) and kinetic indices (k) for the one-electron transfer reactions in charge transfer complex systems indicates the formation of shortlived intermediates between the starting compounds and final Reaction products (in the case of increasing K(AD) values with increasing k(TCE–)) or of several longlived intermediate complexes (in the case of increasing K(AD) values with decreasing k(TCE–).Translated from Teoreticheskaya i Eksperimental'naya Khimiya, Vol. 23, No. 6, pp. 692–699, November–December, 1987. |
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