Internal charge-transfer in a metal-catalyzed oxidative addition reaction turns an inhibitive electric field stimulus to catalytic.

In a metal-catalyzed oxidative addition, an oriented external electric field (EEF) catalyzes the reaction along one direction and inhibits it when applied in the opposite direction. Beyond a threshold value, the inhibitory direction becomes catalyzing by swapping the metal-to-ligand charge transfer (MLCT) to ligand-to-metal charge-transfer (LMCT) or . The change in direction of the charge-transfer mechanism triggers the inversion of the dipole moment along the reaction axis, that results in the resurgence of catalysis.

Two-Way Catalysis in a Diels-Alder Reaction Limits Inhibition Induced by an External Electric Field.

Oriented external electric fields (EEFs) act as catalysts that can induce selectivity in chemical reactions. The responses of the Diels-Alder (DA) reaction between butadiene and ethylene (BDE-DA) as well as cyclopentadiene and ethylene (CPDE-DA) towards EEF stimuli are investigated here using density functional theory (B3LYP) calculations. EEF is a vector that catalyzes the reaction in one direction while inhibiting it in the opposite direction.