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. 2021 Sep 3;11(17):10923-10932.
doi: 10.1021/acscatal.1c02084. Epub 2021 Aug 18.

Electric Fields in Catalysis: From Enzymes to Molecular Catalysts

Nadia G Léonard  1 , Rakia Dhaoui  1 , Teera Chantarojsiri  2 , Jenny Y Yang  1
Affiliations

Electric Fields in Catalysis: From Enzymes to Molecular Catalysts

Nadia G Léonard et al. ACS Catal. .

Abstract

Electric fields underlie all reactions and impact reactivity by interacting with the dipoles and net charges of transition states, products, and reactants to modify the free energy landscape. However, they are rarely given deliberate consideration in synthetic design to rationally control reactivity. This Perspective discusses the commonalities of electric field effects across multiple platforms, from enzymes to molecular catalysts, and identifies practical challenges to applying them in synthetic molecular systems to mediate reactivity.

Keywords: bioinorganic; catalysis; dipoles; electric fields; electrostatics; redox reactions; transition metals.

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Figures

Figure 1.
Figure 1.
Potential impact of electrostatics on reaction energetics.
Figure 2.
Figure 2.
A. Proton shuttle mechanism for HDAC8. B. Depiction of the active site of HDAC8 from a computational study. The system consists of the central Zn2+ ion (gray sphere), substrate (orange), K+ ion (purple sphere), and local residues. Reproduced with permission from ref . Copyright 2016 American Chemical Society.
Figure 3.
Figure 3.
Types of electrostatic interactions at transition metal complexes: A. Supramolecular host, B. Ion-pair interaction, C. Bound cation, D. Charged functional group. M = transition metal; L = ligand; D = ion-pair donor; A = ion-pair acceptor; R± = R′3N+, R′3B−, or Mn+ = nonredox active metal.
Figure 4.
Figure 4.
Electrostatic potential maps of Fe(II) in a salen framework without (top) or with (bottom) a proximal K+ cation. S = CH3CN. Reproduced with permission from ref . Copyright 2019 The Royal Society of Chemistry.
Figure 5.
Figure 5.
Reported homogeneous transition metal complexes with charged functionalities that contribute to changes in electronic structure or reactivity. Left, top-to-bottom: Agapie (refs and 126), Gilbertson (ref 127), Mayer (ref and 131), Groves (refs and 133), Shaik (ref 134), McCrory (ref 136); Right, top-to-bottom: Tomson (ref 140), Savéant (ref 128), Warren (ref 129), Tolman (ref 135), Wiedner (ref 137).
See this image and copyright information in PMC

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