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The second‐order rate constants (k) for reaction of 7‐chloro‐4‐nitrobenzofurazan 1 and 7‐methoxy‐4‐nitrobenzofurazan 2 with a series of nitroalkyl anions and several of para‐substituted phenoxide anions in aqueous solution at 20 °C have been reported. On the basis of the linear novel approach recently designed by Mayr and coworkers, the electrophilicity parameters E at the C‐5 position of the two nitrobenzofurazans 1 and 2 have been quantified and ranked on the comprehensive electrophilicity scale. Mayr's approach was found to correctly predict the rate constants for the addition of phenoxide anions at the C‐5 position of 1 and 2 witting a factor of <2. Analysis of the kinetic measurements using Brønsted's model shows that βnuc values remain remarkably constant for changes in the nature of the substituent and that the σ‐complexation process is associated with high Marcus intrinsic barriers. In addition, satisfactory correlations between the log kexp (kexp values measured in this work for reactions of benzofurazans 1 and 2 with a series of phenoxide anions in aqueous solution at 20 °C) and log kcalcd (kcalcd values calculated from equation 1 using the electrophilicity parameters E of benzofurazans 1 and 2 and the previously published nucleophilicity parameters N and sN of the phenoxide anions) with a slope very close to unity have been obtained and discussed.

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