The regioselectivity in Diels-Alder cycloadditions of #6094C68 fullerene with a triplet ground state
dc.contributor.author
dc.date.accessioned
2019-09-03T06:42:43Z
dc.date.available
2021-04-07T08:03:01Z
dc.date.issued
2019-06-17
dc.identifier.issn
0022-3263
dc.identifier.uri
dc.description.abstract
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
dc.description.sponsorship
Financial 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 grant
dc.format.extent
8 p.
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application/pdf
dc.language.iso
eng
dc.publisher
American Chemical Society (ACS)
dc.relation
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2017-85341-P/ES/AVANCES EN LA REACTIVIDAD DE FULLERENOS Y NANOTUBOS: ESTUDIOS TEORICO-EXPERIMENTALES DE CICLACIONES CATALIZADAS POR METALES DE TRANSICION/
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Versió postprint del document publicat a: https://doi.org/10.1021/acs.joc.9b00921
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© Journal of Organic Chemistry, 2019, vol. 84, núm. 14, p. 9017-9024
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Articles publicats (D-Q)
dc.rights
Tots els drets reservats
dc.source
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
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dc.title
The regioselectivity in Diels-Alder cycloadditions of #6094C68 fullerene with a triplet ground state
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/openAccess
dc.embargo.terms
2020-06-17T00:00:00Z
dc.date.embargoEndDate
info:eu-repo/date/embargoEnd/2020-06-17
dc.type.version
info:eu-repo/semantics/acceptedVersion
dc.identifier.doi
dc.identifier.idgrec
030085
dc.contributor.funder
dc.type.peerreviewed
peer-reviewed
dc.relation.FundingProgramme
dc.relation.ProjectAcronym
dc.identifier.eissn
1520-6904