The role of aromaticity in determining the molecular structure and reactivity of (endohedral metallo)fullerenes

The encapsulation of metal clusters in endohedral metallofullerenes (EMFs) takes place in cages that in most cases are far from being the most stable isomer in the corresponding hollow fullerenes. There exist several possible explanations for the choice of the hosting cages in EMFs, although the fin...

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Autores: Garcia Borràs, Marc, Osuna Oliveras, Sílvia, Luis Luis, Josep Maria, Swart, Marcel, Solà i Puig, Miquel
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2014
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:10256/10328
Acceso en línea:http://hdl.handle.net/10256/10328
Access Level:acceso embargado
Palabra clave:Fullerenes
Ful·lerens
Reaccions químiques
Chemical reactions
Aromaticitat (Química)
Aromaticity (Chemistry)
Bingel-Hirsch, Reacció de
Bingel-Hirsch reaction
id ES_fc142982df0dca01b123eedb7e77963d
oai_identifier_str oai:recercat.cat:10256/10328
network_acronym_str ES
network_name_str España
repository_id_str
dc.title.none.fl_str_mv The role of aromaticity in determining the molecular structure and reactivity of (endohedral metallo)fullerenes
title The role of aromaticity in determining the molecular structure and reactivity of (endohedral metallo)fullerenes
spellingShingle The role of aromaticity in determining the molecular structure and reactivity of (endohedral metallo)fullerenes
Garcia Borràs, Marc
Fullerenes
Ful·lerens
Reaccions químiques
Chemical reactions
Aromaticitat (Química)
Aromaticity (Chemistry)
Bingel-Hirsch, Reacció de
Bingel-Hirsch reaction
title_short The role of aromaticity in determining the molecular structure and reactivity of (endohedral metallo)fullerenes
title_full The role of aromaticity in determining the molecular structure and reactivity of (endohedral metallo)fullerenes
title_fullStr The role of aromaticity in determining the molecular structure and reactivity of (endohedral metallo)fullerenes
title_full_unstemmed The role of aromaticity in determining the molecular structure and reactivity of (endohedral metallo)fullerenes
title_sort The role of aromaticity in determining the molecular structure and reactivity of (endohedral metallo)fullerenes
dc.creator.none.fl_str_mv Garcia Borràs, Marc
Osuna Oliveras, Sílvia
Luis Luis, Josep Maria
Swart, Marcel
Solà i Puig, Miquel
author Garcia Borràs, Marc
author_facet Garcia Borràs, Marc
Osuna Oliveras, Sílvia
Luis Luis, Josep Maria
Swart, Marcel
Solà i Puig, Miquel
author_role author
author2 Osuna Oliveras, Sílvia
Luis Luis, Josep Maria
Swart, Marcel
Solà i Puig, Miquel
author2_role author
author
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 Fullerenes
Ful·lerens
Reaccions químiques
Chemical reactions
Aromaticitat (Química)
Aromaticity (Chemistry)
Bingel-Hirsch, Reacció de
Bingel-Hirsch reaction
topic Fullerenes
Ful·lerens
Reaccions químiques
Chemical reactions
Aromaticitat (Química)
Aromaticity (Chemistry)
Bingel-Hirsch, Reacció de
Bingel-Hirsch reaction
description The encapsulation of metal clusters in endohedral metallofullerenes (EMFs) takes place in cages that in most cases are far from being the most stable isomer in the corresponding hollow fullerenes. There exist several possible explanations for the choice of the hosting cages in EMFs, although the final reasons are actually not totally well understood. Moreover, the reactivity and regioselectivity of (endohedral metallo)fullerenes have in the past decade been shown to be generally dependent on a number of factors, such as the size of the fullerene cage, the type of cluster that is being encapsulated, and the number of electrons that are transferred formally from the cluster to the fullerene cage. Different rationalizations of the observed trends had been proposed, based on bond lengths, pyramidalization angles, shape and energies of (un)occupied orbitals, deformation energies of the cages, or separation distances between the pentagon rings. Recently, in our group we proposed that the quest for the maximum aromaticity (maximum aromaticity criterion) determines the most suitable hosting carbon cage for a given metallic cluster (i.e. EMF stabilization), including those cases where the IPR rule is not fulfilled. Moreover, we suggested that local aromaticity plays a determining role in the reactivity of EMFs, which can be used as a criterion for understanding and predicting the regioselectivity of different reactions such as Diels-Alder cycloadditions or Bingel-Hirsch reactions. This review highlights different aspects of the aromaticity of fullerenes and EMFs, starting from how this can be measured and ending by how it can be used to rationalize and predict their molecular structure and reactivity
publishDate 2014
dc.date.none.fl_str_mv 2014
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/10256/10328
http://hdl.handle.net/10256/10328
url http://hdl.handle.net/10256/10328
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1039/c4cs00040d
info:eu-repo/semantics/altIdentifier/issn/0306-0012
info:eu-repo/semantics/altIdentifier/eissn/1460-4744
info:eu-repo/grantAgreement/MICINN//CTQ2011-23156
info:eu-repo/grantAgreement/MICINN//CTQ2011-25086
AGAUR/2009-2014/2009 SGR-637
AGAUR/2009-2014/2009 SGR-528
info:eu-repo/grantAgreement/EC/FP7/630978
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 Elsevier
publisher.none.fl_str_mv Elsevier
dc.source.none.fl_str_mv © Chemical Society Reviews, 2014, vol. 43, p. 5089-5105
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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spelling The role of aromaticity in determining the molecular structure and reactivity of (endohedral metallo)fullerenesGarcia Borràs, MarcOsuna Oliveras, SílviaLuis Luis, Josep MariaSwart, MarcelSolà i Puig, MiquelFullerenesFul·lerensReaccions químiquesChemical reactionsAromaticitat (Química)Aromaticity (Chemistry)Bingel-Hirsch, Reacció deBingel-Hirsch reactionThe encapsulation of metal clusters in endohedral metallofullerenes (EMFs) takes place in cages that in most cases are far from being the most stable isomer in the corresponding hollow fullerenes. There exist several possible explanations for the choice of the hosting cages in EMFs, although the final reasons are actually not totally well understood. Moreover, the reactivity and regioselectivity of (endohedral metallo)fullerenes have in the past decade been shown to be generally dependent on a number of factors, such as the size of the fullerene cage, the type of cluster that is being encapsulated, and the number of electrons that are transferred formally from the cluster to the fullerene cage. Different rationalizations of the observed trends had been proposed, based on bond lengths, pyramidalization angles, shape and energies of (un)occupied orbitals, deformation energies of the cages, or separation distances between the pentagon rings. Recently, in our group we proposed that the quest for the maximum aromaticity (maximum aromaticity criterion) determines the most suitable hosting carbon cage for a given metallic cluster (i.e. EMF stabilization), including those cases where the IPR rule is not fulfilled. Moreover, we suggested that local aromaticity plays a determining role in the reactivity of EMFs, which can be used as a criterion for understanding and predicting the regioselectivity of different reactions such as Diels-Alder cycloadditions or Bingel-Hirsch reactions. This review highlights different aspects of the aromaticity of fullerenes and EMFs, starting from how this can be measured and ending by how it can be used to rationalize and predict their molecular structure and reactivityThe following organizations are thanked for financial support: the Ministerio de Ciencia e Innovacion (MICINN, project numbers CTQ2011-23156/BQU and CTQ2011-25086/BQU), the Generalitat de Catalunya (projects number 2009SGR637 and 2009SGR528 and Xarxa de Referencia en Quimica Teorica i Computacional), and the FEDER fund (European Fund for Regional Development) for the grant UNGI08-4E-003. M. G.-B. thanks the Spanish MEC for a doctoral fellowship no. AP2010-2517. S.O. thanks the MICINN for the Juan de la Cierva fellowship and the European Community for the CIG project (FP7-PEOPLE-2013-CIG-630978). The authors are also grateful to the computer resources, technical expertise, and assistance provided by the Barcelona Supercomputing Center Centro Nacional de Supercomputacion. Support for the research of M. Sola was received through the ICREA Academia 2009 prize for excellence in research funded by the DIUE of the Generalitat de Catalunya. Excellent service by the Centre de Serveis Cientifics i Academics de Catalunya (CESCA) is gratefully acknowledgedElsevierMinisterio de Ciencia e Innovación (Espanya)Generalitat de Catalunya. Agència de Gestió d'Ajuts Universitaris i de Recercainfoinfo2014info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://hdl.handle.net/10256/10328http://hdl.handle.net/10256/10328© Chemical Society Reviews, 2014, vol. 43, p. 5089-5105Articles 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/10.1039/c4cs00040dinfo:eu-repo/semantics/altIdentifier/issn/0306-0012info:eu-repo/semantics/altIdentifier/eissn/1460-4744info:eu-repo/grantAgreement/MICINN//CTQ2011-23156info:eu-repo/grantAgreement/MICINN//CTQ2011-25086AGAUR/2009-2014/2009 SGR-637AGAUR/2009-2014/2009 SGR-528info:eu-repo/grantAgreement/EC/FP7/630978Tots els drets reservatsinfo:eu-repo/semantics/embargoedAccessoai:recercat.cat:10256/103282026-05-29T05:05:01Z
score 15,198674

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