The regioselectivity in Diels-Alder cycloadditions of #6094C68 fullerene with a triplet ground state

To achieve a full control on the regioselectivity of chemical additions to fullerenes is a major goal in the field of the reactivity of carbon nanostructures. In this work, we computationally analyze the regioselectivity of the Diels-Alder (DA) reaction of cyclopentadiene to the hollow non-isolated...

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Autores: Artigas Ruf, Albert, Fenández López, Israel, Solà i Puig, Miquel
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2019
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:10256/16841
Acceso en línea:http://hdl.handle.net/10256/16841
Access Level:acceso abierto
Palabra clave:Reaccions d'addició
Ful·lerens
Reacció de Diels-Alder
Addition reactions
Fullerenes
Diels-Alder reaction
Reaccions químiques regioselectives
Regioselectivity Chemical reactions
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spelling The regioselectivity in Diels-Alder cycloadditions of #6094C68 fullerene with a triplet ground stateArtigas Ruf, AlbertFenández López, IsraelSolà i Puig, MiquelReaccions d'addicióFul·lerensReacció de Diels-AlderAddition reactionsFullerenesDiels-Alder reactionReaccions químiques regioselectivesRegioselectivity Chemical reactionsTo achieve a full control on the regioselectivity of chemical additions to fullerenes is a major goal in the field of the reactivity of carbon nanostructures. In this work, we computationally analyze the regioselectivity of the Diels-Alder (DA) reaction of cyclopentadiene to the hollow non-isolated pentagon rule (IPR) #6094C68 fullerene, which possesses a triplet ground state. Our aim is to check whether the typically favored [6,6]-addition in fullerenes can be shifted to [5,6] bonds in #6094C68 due to the change in their ground states. Our results show that the [5,5] adduct is the thermodynamic reaction product whereas the kinetic product is the [5,6] bond of type F, adjacent to a pentalene unit. As compared to the singlet state, in the triplet state, the Gibbs barrier for the attack to the [5,6] bond of #6094C68 is reduced by about 5 kcal·mol-1, the DA cycloaddition becoming more regioselective. Our energy decomposition analysis shows that the change of regioselectivity in the DA reaction of hollow fullerenes from the usual [6,6] bond to the [5,6] bond in #6094C68 is driven by higher stabilizing orbital interactions in the latter bond favored by the spin density accumulation around the two pentalene units of the cage. The findings of this investigation complement those of earlier studies on the regioselectivity of IPR fullerenes and endohedral metallofullerenesFinancial support was provided by the Spanish Ministerio de Economía y Competitividad (MINECO) and FEDER (Grants CTQ2016-78205-P and CTQ2016-81797-REDC to I. F. and CTQ2017-85341-P to M. S.), and Catalan DIUE (projects 2017SGR39, ICREA Academia 2014 prize, and XRQTC to M. S.). The FEDER grant UNGI10-4E-801 has also funded this research. A. A. acknowledges the MINECO for a FPI grantAmerican Chemical Society (ACS)Ministerio de Economía y Competitividad (Espanya)info2019info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersionpeer-reviewed8 p.application/pdfhttp://hdl.handle.net/10256/16841http://hdl.handle.net/10256/16841© Journal of Organic Chemistry, 2019, vol. 84, núm. 14, p. 9017-9024Articles publicats (D-Q)Artigas Ruf, Albert Fernández, Israel Solà i Puig, Miquel 2019 The regioselectivity in Diels-Alder cycloadditions of #6094C68 fullerene with a triplet ground state Journal of Organic Chemistry 84 14 9017 9024reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)Inglésinfo:eu-repo/semantics/altIdentifier/doi/10.1021/acs.joc.9b00921info:eu-repo/semantics/altIdentifier/issn/0022-3263info:eu-repo/semantics/altIdentifier/eissn/1520-6904info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2017-85341-PTots els drets reservatsinfo:eu-repo/semantics/openAccessoai:recercat.cat:10256/168412026-05-29T05:05:01Z
dc.title.none.fl_str_mv The regioselectivity in Diels-Alder cycloadditions of #6094C68 fullerene with a triplet ground state
title The regioselectivity in Diels-Alder cycloadditions of #6094C68 fullerene with a triplet ground state
spellingShingle The regioselectivity in Diels-Alder cycloadditions of #6094C68 fullerene with a triplet ground state
Artigas Ruf, Albert
Reaccions d'addició
Ful·lerens
Reacció de Diels-Alder
Addition reactions
Fullerenes
Diels-Alder reaction
Reaccions químiques regioselectives
Regioselectivity Chemical reactions
title_short The regioselectivity in Diels-Alder cycloadditions of #6094C68 fullerene with a triplet ground state
title_full The regioselectivity in Diels-Alder cycloadditions of #6094C68 fullerene with a triplet ground state
title_fullStr The regioselectivity in Diels-Alder cycloadditions of #6094C68 fullerene with a triplet ground state
title_full_unstemmed The regioselectivity in Diels-Alder cycloadditions of #6094C68 fullerene with a triplet ground state
title_sort The regioselectivity in Diels-Alder cycloadditions of #6094C68 fullerene with a triplet ground state
dc.creator.none.fl_str_mv Artigas Ruf, Albert
Fenández López, Israel
Solà i Puig, Miquel
author Artigas Ruf, Albert
author_facet Artigas Ruf, Albert
Fenández López, Israel
Solà i Puig, Miquel
author_role author
author2 Fenández López, Israel
Solà i Puig, Miquel
author2_role author
author
dc.contributor.none.fl_str_mv Ministerio de Economía y Competitividad (Espanya)
dc.subject.none.fl_str_mv Reaccions d'addició
Ful·lerens
Reacció de Diels-Alder
Addition reactions
Fullerenes
Diels-Alder reaction
Reaccions químiques regioselectives
Regioselectivity Chemical reactions
topic Reaccions d'addició
Ful·lerens
Reacció de Diels-Alder
Addition reactions
Fullerenes
Diels-Alder reaction
Reaccions químiques regioselectives
Regioselectivity Chemical reactions
description To achieve a full control on the regioselectivity of chemical additions to fullerenes is a major goal in the field of the reactivity of carbon nanostructures. In this work, we computationally analyze the regioselectivity of the Diels-Alder (DA) reaction of cyclopentadiene to the hollow non-isolated pentagon rule (IPR) #6094C68 fullerene, which possesses a triplet ground state. Our aim is to check whether the typically favored [6,6]-addition in fullerenes can be shifted to [5,6] bonds in #6094C68 due to the change in their ground states. Our results show that the [5,5] adduct is the thermodynamic reaction product whereas the kinetic product is the [5,6] bond of type F, adjacent to a pentalene unit. As compared to the singlet state, in the triplet state, the Gibbs barrier for the attack to the [5,6] bond of #6094C68 is reduced by about 5 kcal·mol-1, the DA cycloaddition becoming more regioselective. Our energy decomposition analysis shows that the change of regioselectivity in the DA reaction of hollow fullerenes from the usual [6,6] bond to the [5,6] bond in #6094C68 is driven by higher stabilizing orbital interactions in the latter bond favored by the spin density accumulation around the two pentalene units of the cage. The findings of this investigation complement those of earlier studies on the regioselectivity of IPR fullerenes and endohedral metallofullerenes
publishDate 2019
dc.date.none.fl_str_mv 2019
info
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
peer-reviewed
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10256/16841
http://hdl.handle.net/10256/16841
url http://hdl.handle.net/10256/16841
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.joc.9b00921
info:eu-repo/semantics/altIdentifier/issn/0022-3263
info:eu-repo/semantics/altIdentifier/eissn/1520-6904
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2017-85341-P
dc.rights.none.fl_str_mv Tots els drets reservats
info:eu-repo/semantics/openAccess
rights_invalid_str_mv Tots els drets reservats
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 8 p.
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society (ACS)
publisher.none.fl_str_mv American Chemical Society (ACS)
dc.source.none.fl_str_mv © Journal of Organic Chemistry, 2019, vol. 84, núm. 14, p. 9017-9024
Articles publicats (D-Q)
Artigas Ruf, Albert Fernández, Israel Solà i Puig, Miquel 2019 The regioselectivity in Diels-Alder cycloadditions of #6094C68 fullerene with a triplet ground state Journal of Organic Chemistry 84 14 9017 9024
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 15,811543

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