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Issue 14, 2018
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Structure and reactivity/selectivity control by oriented-external electric fields

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Abstract

This is a tutorial on use of external-electric-fields (EEFs) as effectors of chemical change. The tutorial instructs readers how to conceptualize and design electric-field effects on bonds, structures, and reactions. Most effects can be comprehended as the field-induced stabilization of ionic structures. Thus, orienting the field along the “bond axis” will facilitate bond breaking. Similarly, orienting the field along the “reaction axis”, the direction in which “electron pairs transform” from reactants- to products-like, will catalyse the reaction. Flipping the field's orientation along the reaction-axis will cause inhibition. Orienting the field off-reaction-axis will control stereo-selectivity and remove forbidden-orbital mixing. Two-directional fields may control both reactivity and selectivity. Increasing the field strength for concerted reactions (e.g., Diels–Alder's) will cause mechanistic-switchover to stepwise mechanisms with ionic intermediates. Examples of bond breaking and control of reactivity/selectivity and mechanisms are presented and analysed from the “ionic perspective”. The tutorial projects the unity of EEF effects, “giving insight and numbers”.

Graphical abstract: Structure and reactivity/selectivity control by oriented-external electric fields

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Publication details

The article was received on 03 May 2018 and first published on 06 Jul 2018


Article type: Tutorial Review
DOI: 10.1039/C8CS00354H
Citation: Chem. Soc. Rev., 2018,47, 5125-5145
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    Structure and reactivity/selectivity control by oriented-external electric fields

    S. Shaik, R. Ramanan, D. Danovich and D. Mandal, Chem. Soc. Rev., 2018, 47, 5125
    DOI: 10.1039/C8CS00354H

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