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

Karthik GopakumarVivekananda SamantarayMithun Kumar PrustyLopita SwainRajeev Ramanan
Published in: Chemical communications (Cambridge, England) (2023)
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 vice versa . 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. The charge-transfer mechanism in metal-catalyzed oxidative addition is tunable by EEF.
Keyphrases
  • room temperature
  • contrast enhanced
  • electron transfer