External electric field effects on chemical structure and reactivity,Wiley Interdisciplinary Reviews: Computational Molecular Science

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External electric field effects on chemical structure and reactivity
Wiley Interdisciplinary Reviews: Computational Molecular Science ( IF 16.8 ) Pub Date : 2019-07-26 , DOI: 10.1002/wcms.1438
Thijs Stuyver _{1,

2} , David Danovich ₁ , Jyothish Joy ₁ , Sason Shaik ₁

Affiliation

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.

中文翻译：

外部电场对化学结构和反应性的影响

近年来，外部电场（EEF）作为化学变化的新型效应器引起了人们的关注。EEF直接影响分子系统的结构。例如，沿着特定的键轴对齐电场会导致键的缩短或伸长（并最终导致键断裂）。此外，EEF可以对化学反应性进行前所未有的控制。沿所谓的“反应轴”定向电场，即电子从反应物向产物转化过程中电子重组的方向，导致催化或抑制，并可能导致机械反应从协同反应转变为逐步反应。离轴方向的取向可控制反应的立体选择性，并禁用禁轨道混合。双向字段可控制反应性和选择性。在这篇高级综述中，我们提供了这个快速发展的研究领域的概述，重点是EEF效应的价键建模及其提供的见解。我们将考虑各种各样的示例，并将贯穿整个实验。最后，我们提供一些观点，在这些观点中，我们假设随着实验技术的不断成熟，EEF可能会成为普遍适用的“快速转换”工具，以促进精细的化学合成。

更新日期：2019-11-18

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