Electrochemical Reduction of Substituted Anthracenes

Abstract

Abstract A systematic investigation of the electrochemical reduction of substituted anthracenes in N,N ‐dimethylformamidc has unveiled the reductive properties of the aromatic compounds. For the anthracenes with a reversible first reduction, the redox potential exhibits linearity vs a value of the Hammett equation. For anthracenes with an irreversible first reduction, the electron transfer and chemical reaction occur via either a sequential or a concerted pathway. When the irreversible first reduction occurs at a potential more negative than E 1/2 calculated from the σ value, the reaction occurs via a sequential pathway, such as for 9‐chloroanthracene. When the irreversible first reduction occurs at a potential more positive than the expected E 1/2 , the reaction occurs via a concerted mechanism of electron transfer and bond breaking, such as for 9‐chloromethylanthracenc. The displacement of the halide results in the parent polyaromatic hydrocarbons, as in dicated by the spectroelectrochemical method.