Influence of the Charge on the Reactivity of Azafullerenes
dc.contributor.author
dc.date.accessioned
2018-12-20T10:33:47Z
dc.date.available
2021-04-07T08:03:00Z
dc.date.issued
2018-11-15
dc.identifier.issn
1463-9076
dc.identifier.uri
dc.description.abstract
The influence of the charge on the Diels-Alder reactivity of azafullerenes (C59N+ and C59N-) has been computationally explored by means of Density Functional Theory calculations. In addition, the regioselectivity of the process has been investigated and compared to the analogous cycloaddition reaction involving the parent neutral azahydro[60]fullerene C59NH. It is found that the [4+2]-cycloaddition reaction between C59N+ and cyclopentadiene, which occurs concertedly through a synchronous transition state, proceeds with a lower activation barrier and is more exothermic than the analogous process involving C59NH. In contrast, the anionic C59N- counterpart is clearly less reactive. This reactivity trend is quantitatively analyzed in detail by means of the Activation Strain Model of reactivity in combination with the Energy Decomposition Analysis method. It is found that the frontier molecular orbital interactions are not responsible for the observed reactivity trend but the Pauli repulsion between closed-shells mainly governs the transformation
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.
Y. G.-R. acknowledges the MINECO for a FPI grant
dc.format.extent
8 p.
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
Royal Society of Chemistry (RSC)
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/10.1039/C8CP06031B
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© Physical Chemistry Chemical Physics, 2018, vol. 20, núm. 44, p. 28011-28018
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Articles publicats (D-Q)
dc.rights
Tots els drets reservats
dc.source
García Rodeja, Yago Solà i Puig, Miquel Fernández, Israel 2018 Influence of the Charge on the Reactivity of Azafullerenes Physical Chemistry Chemical Physics 20 44 28011 28018
dc.title
Influence of the Charge on the Reactivity of Azafullerenes
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/openAccess
dc.embargo.terms
2019-11-15T00:00:00Z
dc.date.embargoEndDate
info:eu-repo/date/embargoEnd/2019-11-15
dc.type.version
info:eu-repo/semantics/acceptedVersion
dc.identifier.doi
dc.identifier.idgrec
029165
dc.contributor.funder
dc.type.peerreviewed
peer-reviewed
dc.relation.FundingProgramme
dc.relation.ProjectAcronym
dc.identifier.eissn
1463-9084