Influence of polarity of medium on the nature of charge transfer complex,kinetics, and mechanism of reaction with a one-electron transfer in a tetracyanoethylene-n-alkyl-substituted aniline system

The influence of the polarity of the medium (B, ) on the thermodynamic characteristics of the formation of a charge transfer complex (CTC) and one electron transfer from a donor D to and acceptor A was studied in N-alkyl-substituted aniline (D) — tetracyanoethylene (A) systems. It was shown that in systems with CTC in which [B]/[D] 1, the limiting step in the reaction with one electron transfer in weakly polar solvents (<20) is the formation of molecular (AD), and in strongly polar sovents (>20), of ionic (AD) CTC. A correlation was established between the spectral (VCT) characteristics of the formation of the CTC and the kinetic parameters (k_eff) of one electron transfer reaction and degrees of charge transfer in molecular and ionic CTC were determined.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 2, pp. 167–173, March–April, 1989.