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Electric fields have been used to control and direct chemical reactions in biochemistry and enzymatic catalysis, yet directly applying external electric fields to activate reactions in bulk solution and to characterize them ex situ remains a challenge. Here we utilize the scanning tunneling microscope-based break-junction technique to investigate the electric field driven homolytic cleavage of the radical initiator 4-(methylthio)benzoic peroxyanhydride at ambient temperatures in bulk solution, without the use of co-initiators or photochemical activators. Through time-dependent ex situ quantification by high performance liquid chromatography using a UV-vis detector, we find that the electric field catalyzes the reaction. Importantly, we demonstrate that the reaction rate in a field increases linearly with the solvent dielectric constant. Using density functional theory calculations, we show that the applied electric field decreases the dissociation energy of the O–O bond and stabilizes the product relative to the reactant due to their different dipole moments. 

The formation of carbon–carbon bonds with transition metal reagents serves as a cornerstone of organic synthesis. Here, we show that the reactivity of an otherwise kinetically inert transition metal complex can be induced by an external electric field to affect a coupling reaction. These results highlight the importance of electric field effects in reaction chemistry and offers a new strategy to modulate organometallic reactivity.