Electro-Inductive Effect: Electrodes as Functional Groups with Tunable Electronic Properties

Abstract

In place of functional groups that impose different inductive effects, we immobilize molecules carrying thiol groups on a gold electrode. By applying different voltages, the properties of the immobilized molecules can be tuned. The base-catalyzed saponification of benzoic esters is fully inhibited by applying a mildly negative voltage of -0.25 volt versus open circuit potential. Furthermore, the rate of a Suzuki-Miyaura cross-coupling reaction can be changed by applying a voltage when the arylhalide substrate is immobilized on a gold electrode. Finally, a two-step carboxylic acid amidation is shown to benefit from a switch in applied voltage between addition of a carbodiimide coupling reagent and introduction of the amine.