Why do cycloaddition reactions involving C60 prefer [6,6] over [5,6] bonds?

The origin of the experimentally known preference for [6,6] over [5,6] bonds in cycloaddition reactions involving C60 has been computationally explored. To this end, the Diels-Alder reaction between cyclopentadiene and C60 has been analysed by means of the recently introduced activation strain model...

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Autores: Fenández López, Israel, Solà i Puig, Miquel, Bickelhaupt, F. Matthias
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2013
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:10256/11433
Acceso en línea:http://hdl.handle.net/10256/11433
Access Level:acceso embargado
Palabra clave:Reaccions d'addició
Addition reactions
Funcional de densitat, Teoria del
Density functionals
Diels-Alder, Reacció de
Diels-Alder reaction
Fullerenes
Ful·lerens
Ciclització (Química)
Ring formation (Chemistry)
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spelling Why do cycloaddition reactions involving C60 prefer [6,6] over [5,6] bonds?Fenández López, IsraelSolà i Puig, MiquelBickelhaupt, F. MatthiasReaccions d'addicióAddition reactionsFuncional de densitat, Teoria delDensity functionalsDiels-Alder, Reacció deDiels-Alder reactionFullerenesFul·lerensCiclització (Química)Ring formation (Chemistry)The origin of the experimentally known preference for [6,6] over [5,6] bonds in cycloaddition reactions involving C60 has been computationally explored. To this end, the Diels-Alder reaction between cyclopentadiene and C60 has been analysed by means of the recently introduced activation strain model of reactivity in combination with the energy decomposition analysis method. Other issues, such as the aromaticity of the corresponding transition states, have also been considered. These results indicate that the major factor controlling the observed regioselectivity is the more stabilising interaction between the deformed reactants in the [6,6] reaction pathway along the entire reaction coordinate. Why [6,6]? The preference for [6,6] over [5,6] bonds in cycloaddition reactions involving C60 is experimentally well-established (see figure). However, the reasons (i.e., physical factors) behind this preference are so far completely unknown. By means of the recently introduced activation strain model of reactivity in combination with the energy decomposition analysis method, a definite answer to the question in the title is providedWe are grateful for financial support from the Spanish MICINN (grants CTQ2010-20714-C02-01, Consolider-Ingenio 2010, and CSD2007-00006 to I. F. and CTQ2011-23156/BQU to M. S.), CAM (grant S2009/PPQ-1634 to I. F.), Catalan DIUE (projects 2009SGR637 and XRQTC to M. S.), the FEDER fund for the grant UNGI08-4E-003 to M. S., the National Research School Combination-Catalysis (NRSC-C), and The Netherlands Organization for Scientific Research (NWO/CW and NWO/NCF). Support for the research of M. S. was received through the ICREA Academia 2009 prize of the Catalan DIUEWiley-VCH VerlagMinisterio de Ciencia e Innovación (Espanya)Generalitat de Catalunya. Agència de Gestió d'Ajuts Universitaris i de Recercainfoinfo2013info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://hdl.handle.net/10256/11433http://hdl.handle.net/10256/11433© Chemistry - A European Journal, 2013, vol. 19, núm. 23, p. 7416-7422Articles publicats (D-Q)reponame: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/10.1002/chem.201300648info:eu-repo/semantics/altIdentifier/issn/0947-6539info:eu-repo/semantics/altIdentifier/eissn/1521-3765info:eu-repo/grantAgreement/MICINN//CTQ2011-23156AGAUR/2009-2014/2009 SGR-637Tots els drets reservatsinfo:eu-repo/semantics/embargoedAccessoai:recercat.cat:10256/114332026-05-29T05:05:01Z
dc.title.none.fl_str_mv Why do cycloaddition reactions involving C60 prefer [6,6] over [5,6] bonds?
title Why do cycloaddition reactions involving C60 prefer [6,6] over [5,6] bonds?
spellingShingle Why do cycloaddition reactions involving C60 prefer [6,6] over [5,6] bonds?
Fenández López, Israel
Reaccions d'addició
Addition reactions
Funcional de densitat, Teoria del
Density functionals
Diels-Alder, Reacció de
Diels-Alder reaction
Fullerenes
Ful·lerens
Ciclització (Química)
Ring formation (Chemistry)
title_short Why do cycloaddition reactions involving C60 prefer [6,6] over [5,6] bonds?
title_full Why do cycloaddition reactions involving C60 prefer [6,6] over [5,6] bonds?
title_fullStr Why do cycloaddition reactions involving C60 prefer [6,6] over [5,6] bonds?
title_full_unstemmed Why do cycloaddition reactions involving C60 prefer [6,6] over [5,6] bonds?
title_sort Why do cycloaddition reactions involving C60 prefer [6,6] over [5,6] bonds?
dc.creator.none.fl_str_mv Fenández López, Israel
Solà i Puig, Miquel
Bickelhaupt, F. Matthias
author Fenández López, Israel
author_facet Fenández López, Israel
Solà i Puig, Miquel
Bickelhaupt, F. Matthias
author_role author
author2 Solà i Puig, Miquel
Bickelhaupt, F. Matthias
author2_role author
author
dc.contributor.none.fl_str_mv Ministerio de Ciencia e Innovación (Espanya)
Generalitat de Catalunya. Agència de Gestió d'Ajuts Universitaris i de Recerca
dc.subject.none.fl_str_mv Reaccions d'addició
Addition reactions
Funcional de densitat, Teoria del
Density functionals
Diels-Alder, Reacció de
Diels-Alder reaction
Fullerenes
Ful·lerens
Ciclització (Química)
Ring formation (Chemistry)
topic Reaccions d'addició
Addition reactions
Funcional de densitat, Teoria del
Density functionals
Diels-Alder, Reacció de
Diels-Alder reaction
Fullerenes
Ful·lerens
Ciclització (Química)
Ring formation (Chemistry)
description The origin of the experimentally known preference for [6,6] over [5,6] bonds in cycloaddition reactions involving C60 has been computationally explored. To this end, the Diels-Alder reaction between cyclopentadiene and C60 has been analysed by means of the recently introduced activation strain model of reactivity in combination with the energy decomposition analysis method. Other issues, such as the aromaticity of the corresponding transition states, have also been considered. These results indicate that the major factor controlling the observed regioselectivity is the more stabilising interaction between the deformed reactants in the [6,6] reaction pathway along the entire reaction coordinate. Why [6,6]? The preference for [6,6] over [5,6] bonds in cycloaddition reactions involving C60 is experimentally well-established (see figure). However, the reasons (i.e., physical factors) behind this preference are so far completely unknown. By means of the recently introduced activation strain model of reactivity in combination with the energy decomposition analysis method, a definite answer to the question in the title is provided
publishDate 2013
dc.date.none.fl_str_mv 2013
info
info
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10256/11433
http://hdl.handle.net/10256/11433
url http://hdl.handle.net/10256/11433
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1002/chem.201300648
info:eu-repo/semantics/altIdentifier/issn/0947-6539
info:eu-repo/semantics/altIdentifier/eissn/1521-3765
info:eu-repo/grantAgreement/MICINN//CTQ2011-23156
AGAUR/2009-2014/2009 SGR-637
dc.rights.none.fl_str_mv Tots els drets reservats
info:eu-repo/semantics/embargoedAccess
rights_invalid_str_mv Tots els drets reservats
eu_rights_str_mv embargoedAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Wiley-VCH Verlag
publisher.none.fl_str_mv Wiley-VCH Verlag
dc.source.none.fl_str_mv © Chemistry - A European Journal, 2013, vol. 19, núm. 23, p. 7416-7422
Articles publicats (D-Q)
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 15.812429

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