Prof. MU-HYUN "Mookie" BAIK, Center for Catalytic Hydrocarbon Functionalizations (CCHF) – Institute for Basic Science (IBS), Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon, Korea
Title: The Electro-Inductive Effect
Abstract:
Predicting the outcome of chemical reactions by constructing quantum chemical computer models is exceedingly difficult. Although we have made tremendous progress recently, truly predictive computational chemistry remains a largely unfulfilled dream at the moment. How do we move forward? In addition to improving computer models, we reasoned that we should design experiments that are more “computer-friendly”. For example, controlling the chemical and physical properties of a molecule by decorating it with functional groups that impose different inductive effects is common, but highly unfriendly to computer models, because changing atoms creates a number of computational challenges. In an effort to deal with this, we questioned if there is not a better way of imposing inductive effects on molecules that does not change the composition of the molecular system.
What if we were to immobilize the parent molecule onto an electrode, for example by installing a thiol group to the molecule and forming a self-assembled monolayer on a gold surface? When we apply a voltage, will the electronic property of the immobilized molecule change? Could an electrode act as a functional group that is electron-donating or electron-withdrawing groups, depending on the sign of the voltage applied?
As a proof of principle, we show that the base-catalyzed saponification of benzoic ester can be shut down completely by applying a negative voltage, while it can be accelerated by using a positive voltage. Furthermore, we found that the Suzuki-Miyaura cross-coupling reaction can be affected by the voltage when the arylhalide substrate of the reaction is immobilized on a gold electrode.
