Electrostatic catalysis of a Diels-Alder reaction

It is often thought that the ability to control reaction rates with an applied electrical potential gradient is unique to redox systems. However, recent theoretical studies suggest that oriented electric fields could affect the outcomes of a range of chemical reactions, regardless of whether a redox...

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Autores: Aragonès, Albert C., Haworth, Naomi, Darwish, Nadim, Ciampi, Simone, Bloomfield, Nathaniel J., Wallace, Gordon G., Díez Pérez, Ismael, Coote, Michelle L.
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2016
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:2445/181441
Acceso en línea:https://hdl.handle.net/2445/181441
Access Level:acceso abierto
Palabra clave:Electroestàtica
Catàlisi
Reacció de Diels-Alder
Electrostatics
Catalysis
Diels-Alder reaction
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spelling Electrostatic catalysis of a Diels-Alder reactionAragonès, Albert C.Haworth, NaomiDarwish, NadimCiampi, SimoneBloomfield, Nathaniel J.Wallace, Gordon G.Díez Pérez, IsmaelCoote, Michelle L.ElectroestàticaCatàlisiReacció de Diels-AlderElectrostaticsCatalysisDiels-Alder reactionIt is often thought that the ability to control reaction rates with an applied electrical potential gradient is unique to redox systems. However, recent theoretical studies suggest that oriented electric fields could affect the outcomes of a range of chemical reactions, regardless of whether a redox system is involved(1-4). This possibility arises because many formally covalent species can be stabilized via minor charge-separated resonance contributors. When an applied electric field is aligned in such a way as to electrostatically stabilize one of these minor forms, the degree of resonance increases, resulting in the overall stabilization of the molecule or transition state. This means that it should be possible to manipulate the kinetics and thermodynamics of non-redox processes using an external electric field, as long as the orientation of the approaching reactants with respect to the field stimulus can be controlled. Here, we provide experimental evidence that the formation of carboncarbon bonds is accelerated by an electric field. We have designed a surface model system to probe the Diels-Alder reaction, and coupled it with a scanning tunnelling microscopy break-junction approach(5-7). This technique, performed at the single-molecule level, is perfectly suited to deliver an electric-field stimulus across approaching reactants. We find a fivefold increase in the frequency of formation of single-molecule junctions, resulting from the reaction that occurs when the electric field is present and aligned so as to favour electron flow from the dienophile to the diene. Our results are qualitatively consistent with those predicted by quantum-chemical calculations in a theoretical model of this system, and herald a new approach to chemical catalysis.Nature Publishing Group2021202120162021info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersion4 p.application/pdfhttps://hdl.handle.net/2445/181441Articles publicats en revistes (Ciència dels Materials i Química Física)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)InglésVersió postprint del document publicat a: https://doi.org/10.1038/nature16989Nature, 2016, vol. 531, p. 88-91https://doi.org/10.1038/nature16989(c) Nature Publishing Group, 2016info:eu-repo/semantics/openAccessoai:recercat.cat:2445/1814412026-05-29T05:05:01Z
dc.title.none.fl_str_mv Electrostatic catalysis of a Diels-Alder reaction
title Electrostatic catalysis of a Diels-Alder reaction
spellingShingle Electrostatic catalysis of a Diels-Alder reaction
Aragonès, Albert C.
Electroestàtica
Catàlisi
Reacció de Diels-Alder
Electrostatics
Catalysis
Diels-Alder reaction
title_short Electrostatic catalysis of a Diels-Alder reaction
title_full Electrostatic catalysis of a Diels-Alder reaction
title_fullStr Electrostatic catalysis of a Diels-Alder reaction
title_full_unstemmed Electrostatic catalysis of a Diels-Alder reaction
title_sort Electrostatic catalysis of a Diels-Alder reaction
dc.creator.none.fl_str_mv Aragonès, Albert C.
Haworth, Naomi
Darwish, Nadim
Ciampi, Simone
Bloomfield, Nathaniel J.
Wallace, Gordon G.
Díez Pérez, Ismael
Coote, Michelle L.
author Aragonès, Albert C.
author_facet Aragonès, Albert C.
Haworth, Naomi
Darwish, Nadim
Ciampi, Simone
Bloomfield, Nathaniel J.
Wallace, Gordon G.
Díez Pérez, Ismael
Coote, Michelle L.
author_role author
author2 Haworth, Naomi
Darwish, Nadim
Ciampi, Simone
Bloomfield, Nathaniel J.
Wallace, Gordon G.
Díez Pérez, Ismael
Coote, Michelle L.
author2_role author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Electroestàtica
Catàlisi
Reacció de Diels-Alder
Electrostatics
Catalysis
Diels-Alder reaction
topic Electroestàtica
Catàlisi
Reacció de Diels-Alder
Electrostatics
Catalysis
Diels-Alder reaction
description It is often thought that the ability to control reaction rates with an applied electrical potential gradient is unique to redox systems. However, recent theoretical studies suggest that oriented electric fields could affect the outcomes of a range of chemical reactions, regardless of whether a redox system is involved(1-4). This possibility arises because many formally covalent species can be stabilized via minor charge-separated resonance contributors. When an applied electric field is aligned in such a way as to electrostatically stabilize one of these minor forms, the degree of resonance increases, resulting in the overall stabilization of the molecule or transition state. This means that it should be possible to manipulate the kinetics and thermodynamics of non-redox processes using an external electric field, as long as the orientation of the approaching reactants with respect to the field stimulus can be controlled. Here, we provide experimental evidence that the formation of carboncarbon bonds is accelerated by an electric field. We have designed a surface model system to probe the Diels-Alder reaction, and coupled it with a scanning tunnelling microscopy break-junction approach(5-7). This technique, performed at the single-molecule level, is perfectly suited to deliver an electric-field stimulus across approaching reactants. We find a fivefold increase in the frequency of formation of single-molecule junctions, resulting from the reaction that occurs when the electric field is present and aligned so as to favour electron flow from the dienophile to the diene. Our results are qualitatively consistent with those predicted by quantum-chemical calculations in a theoretical model of this system, and herald a new approach to chemical catalysis.
publishDate 2016
dc.date.none.fl_str_mv 2016
2021
2021
2021
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv https://hdl.handle.net/2445/181441
url https://hdl.handle.net/2445/181441
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Versió postprint del document publicat a: https://doi.org/10.1038/nature16989
Nature, 2016, vol. 531, p. 88-91
https://doi.org/10.1038/nature16989
dc.rights.none.fl_str_mv (c) Nature Publishing Group, 2016
info:eu-repo/semantics/openAccess
rights_invalid_str_mv (c) Nature Publishing Group, 2016
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 4 p.
application/pdf
dc.publisher.none.fl_str_mv Nature Publishing Group
publisher.none.fl_str_mv Nature Publishing Group
dc.source.none.fl_str_mv Articles publicats en revistes (Ciència dels Materials i Química Física)
reponame:Recercat. Dipósit de la Recerca de Catalunya
instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
instname_str Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
reponame_str Recercat. Dipósit de la Recerca de Catalunya
collection Recercat. Dipósit de la Recerca de Catalunya
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15.812455

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