Ebulliometric and spectroscopic kinetic studies on the reaction between tetracyanoethylene and NN-dimethylaniline
Abstract
The equilibrium constant for the 1 :1 charge-transfer complex between NN-dimethylaniline (DMN) and tetracyanoethylene (TCNE) in dichloromethane has been determiend by Benesi–Hildebrand and equimolar methods. The second-order rate constants, k2, for the DMN–TCNE reaction increase with increasing amine concentration. This suggests that the charg-transfer complex is an intermediate in the reaction sequence and the rate constant, kc, corrected on the basis of this mechanism does not vary with concentration. The Arrhenius plot, using the kc values obtained from the three experimental methods, is a good straight line. Evidence is also presented for the reversibility of the charge-transfer complex →σ-complex step.