The electrochemical reduction of the title compounds, 2a and 3a, and 7,7,8,8-tetracyanoquinodimethane, 1a, was studied in acetonitrile. The reduction of la shows normal ordering of potentials, i.e., the potential for insertion of the first electron, E degrees(1), is more positive than the potential for the second step of reduction, E degrees(2). Thus, E degrees(1) - E degrees(2) > 0. By contrast, 2a and 3a show inversion of potentials where introduction of the second electron occurs with greater ease than the first (E degrees(1) - E degrees(2) < 0). The extent of inversion has been determined by simulation of the cyclic voltammograms obtained at 298 and 257 K. Electron paramagnetic resonance measurements at room temperature of solutions containing equimolar mixtures of the neutral and dianion allow determination of the concentration of anion radicals from which the disproportionation equilibrium constant and E degrees(1) - E degrees(2) can be calculated. The results were in good agreement with the voltammetric determinations. Calculations were conducted to characterize the structural changes accompanying reduction to the anion radical and dianion forms. Fast scan experiments at low temperatures (up to 10 000 V/s at 257 K; 500 V/s at 233 K) were conducted in an attempt to detect intermediates in the reduction, but none was found. Thus, it is not possible to state whether structural change and electron transfer are concerted or occur in discrete steps.