Reduction potentials of various aromatic hydrocarbons and their univalent anions

Abstract

Potentiometric titrations of solutions of various aromatic hydrocarbons in 1,2‐dimethoxyethane and tetrahydrofuran with a solution of biphenylsodium have shown chemical reduction to proceed in two stages: equation image The reduction potentials of the aromatic hydrocarbons, calculated from the potentiometric curve, are in good agreement with the half‐wave potentials obtained from polarographic reductions in 96% dioxan‐water. The standard potentials of the first reduction step expressed in Volts against the standard potential of biphenyl fit the following equation: with γ = ‐ 2.19 ± 0.059 e.V. (2 × stand. dev. from mean) in which a stands for the root of the m.o. secular equation (overlap S = 0.25 included) corresponding to the lowest non‐occupied π‐orbital of the hydrocarbon and γ is the resonance‐parameter.The electrochemical series of aromatic hydrocarbons including a rough estimate of the standard potential of sodium in 1,2‐dimethoxyethane and the mechanism of chemical reduction in inert and proton‐active solvents are discussed.