Oxidation potential as a measure of the effect of environment on the reactivity of anionic nucleophiles

Abstract
The irreversible anodic peak potential of anionic nucleophiles has been shown to be linearly correlated with various measures of their nucleophilic reactivity, including rates of SN2 and SNAr reactions as well as addition to Michael acceptors. The correlations incorporate both changes in the nature of the solvent and the identity of the counter ion. The nucleophiles considered were iodide, azide, cyanide, 4-cyanophenolate, the anion of 2-mercaptobenzoxazole and the anion of ethyl nitroacetate. It is suggested that the oxidation potential can be used as an easily measurable predictor of the effect of solution environment on nucleophilic reactivity.

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