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Oriented electric fields as future smart reagents in chemistry

Nature Chemistry volume 8, pages 1091–1098 (2016)Cite this article

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Abstract

Oriented external electric fields (OEEFs) as 'smart reagents' are no longer a theoretical dream. Here, we discuss the wide-ranging potential of using OEEFs to catalyse and control a variety of non-redox reactions and impart selectivity at will. An OEEF along the direction of electron reorganization (the so-called reaction axis) will catalyse nonpolar reactions by orders of magnitude, control regioselectivity and induce spin-state selectivity. Simply flipping the direction of the OEEF or orienting it off of the reaction axis, will control at will the endo/exo ratio in Diels–Alder reactions and steps in enzymatic cycles. This Perspective highlights these outcomes using theoretical results for hydrogen abstraction reactions, epoxidation of double bonds, C–C bond forming reactions, proton transfers and the cycle of the enzyme cytochrome P450, as well as recent experimental data. We postulate that, as experimental techniques mature, chemical syntheses may become an exercise in zapping oriented molecules with OEEFs.

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Figure 1: MO and VB analyses of the manner by which an OEEF, oriented along the bond axis, generates charge distributions and dipole moments in two homonuclear bonds, H–H and Li–Li.
Figure 2: A z-oriented OEEF affects the bond activation reactions of propene, mediated by an iron-oxo Por radical cation model species (CpdI) of the enzyme cytochrome P450.
Figure 3: A z-oriented OEEF causes selective bond activations of propene by Cpd I, such that either C–H hydroxylation or C=C epoxidation can be produced at will.
Figure 4: A negatively oriented z-OEEF drastically lowers the C–H hydroxylation barriers in the reactions between the two spin states of an iron-oxo complex (TMC(SR)FeO+) and cyclohexane, and creates product- and spin-state selectivities in the quintet state's hydroxylation process.
Figure 5: VB diagrams showing the construction of the energy profiles (brown) for a Diels–Alder reaction between generic diene and dienophile, and leading to predictions of z-OEEF effects on catalysis/inhibition and mechanistic crossover in the reactions.
Figure 6: Computational results showing that OEEFs induce catalysis, inhibition, and endo/exo selectivity in the reaction of cyclopentadiene and maleic anhydride.
Figure 7: The single-molecule experiment1 showing catalysis of a Diels–Alder reaction by an OEEF, created by a bias voltage between the STM tip and the electrode.

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  1. Institute of Chemistry and The Lise Meitner-Minerva Center for Computational Quantum Chemistry, Hebrew University of Jerusalem, Jerusalem, 91904, Israel

    Sason Shaik, Debasish Mandal & Rajeev Ramanan

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Correspondence to Sason Shaik.

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Shaik, S., Mandal, D. & Ramanan, R. Oriented electric fields as future smart reagents in chemistry. Nature Chem 8, 1091–1098 (2016). https://doi.org/10.1038/nchem.2651

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