Control of Reversible Oxidative Addition/Reductive Elimination of Surface-Attached Catalysts by External Electric Fields.

Abstract

We demonstrate that applied electric fields at interfaces can control the oxidative addition/reductive elimination equilibria of surface-attached molecular catalysts without any synthetic modification. Density functional theory (DFT) calculations show that the oxidative addition of HCl to a Co complex is "field switchable", being favorable under negative fields but unfavorable under sufficiently positive fields. Extending the analysis to different substrates (O₂, H₂) and metal centers (Rh, Ir) reveals consistent trends in the magnitude of the electric field effect: Co > Rh ≈ Ir and HCl > O₂ > H₂. Our analysis indicates that these field-dependent effects are driven by changes in the permanent dipole moment, offering key insights for the design of field-controllable catalytic systems. This framework presents a novel strategy to overcome the "Goldilocks problem" of balancing competing catalytic steps by leveraging applied electric fields to dynamically tune catalytic reactivity in situ.