Voltammetric and Coulometric Studies of the Mechanism of Electrohydrodimerization of Diethyl Fumarate in Dimethylformamide Solutions

Abstract

The reduction of diethyl fumarate (DEF) in tetra‐n‐butylammonium iodide (TBAI)‐dimethylformamide (DMF) solutions at a platinum electrode has been studied by cyclic voltammetry, double potential step chronoamperometry, and controlled potential coulometry. The chronoamperometric response for several possible mechanisms of electrohydrodimerization has been obtained by digital simulation techniques, and a method for distinguishing among the mechanisms suggested. Results of double potential step chronoamperometric experiments strongly support a mechanism where the electrochemically generated anion radicals undergo a second‐order dimerization reaction. Controlled potential electrolysis results give evidence for a bulk polymerization reaction in the absence of proton donor; protonation in the presence of hydroquinones; and good efficiency to the hydrodimer product in the presence of lithium perchlorate trihydrate.