TY - JOUR
T1 - External electric field effects on chemical structure and reactivity
AU - Stuyver, Thijs
AU - Danovich, David
AU - Joy, Jyothish
AU - Shaik, Sason
N1 - Publisher Copyright:
© 2019 Wiley Periodicals, Inc.
PY - 2020/3/1
Y1 - 2020/3/1
N2 - In recent years, external electric fields (EEFs) have captured some spotlight as novel effectors of chemical change. EEFs directly impact the structure of molecular systems. For example, aligning an electric field along a specific bond-axis leads to either shortening or elongation of the bond (and ultimately bond breaking). Furthermore, EEFs enable unprecedented control over chemical reactivity. Orienting an electric field along the so-called “reaction-axis,” the direction in which the electrons reorganize during the conversion from reactant to product, leads to catalysis or inhibition and can induce mechanistic crossover from concerted to stepwise reactions. Off-reaction-axis orientation enables control over the stereoselectivity of reactions and disables forbidden–orbital mixing. Two-directional fields enable control over both reactivity and selectivity. In this advanced review, we offer an overview of this rapidly evolving research field with a focus on the valence bond modeling of EEF effects and the insight it offers. A wide variety of examples will be considered and a link to the experiment will be made throughout. We end by offering some perspectives in which we postulate that, as experimental techniques continue to mature, EEFs could potentially become a generally applicable “zapping” tool to facilitate elaborate chemical syntheses. This article is categorized under:. Structure and Mechanism > Reaction Mechanisms and Catalysis.
AB - In recent years, external electric fields (EEFs) have captured some spotlight as novel effectors of chemical change. EEFs directly impact the structure of molecular systems. For example, aligning an electric field along a specific bond-axis leads to either shortening or elongation of the bond (and ultimately bond breaking). Furthermore, EEFs enable unprecedented control over chemical reactivity. Orienting an electric field along the so-called “reaction-axis,” the direction in which the electrons reorganize during the conversion from reactant to product, leads to catalysis or inhibition and can induce mechanistic crossover from concerted to stepwise reactions. Off-reaction-axis orientation enables control over the stereoselectivity of reactions and disables forbidden–orbital mixing. Two-directional fields enable control over both reactivity and selectivity. In this advanced review, we offer an overview of this rapidly evolving research field with a focus on the valence bond modeling of EEF effects and the insight it offers. A wide variety of examples will be considered and a link to the experiment will be made throughout. We end by offering some perspectives in which we postulate that, as experimental techniques continue to mature, EEFs could potentially become a generally applicable “zapping” tool to facilitate elaborate chemical syntheses. This article is categorized under:. Structure and Mechanism > Reaction Mechanisms and Catalysis.
KW - electric field catalysis
KW - external electric fields
KW - valence bond theory
UR - http://www.scopus.com/inward/record.url?scp=85070229828&partnerID=8YFLogxK
U2 - 10.1002/wcms.1438
DO - 10.1002/wcms.1438
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AN - SCOPUS:85070229828
SN - 1759-0876
VL - 10
JO - Wiley Interdisciplinary Reviews: Computational Molecular Science
JF - Wiley Interdisciplinary Reviews: Computational Molecular Science
IS - 2
M1 - e1438
ER -