The Frozen Cage Model: A Computationally Low-Cost Tool for Predicting the Exohedral Regioselectivity of Cycloaddition Reactions Involving Endohedral Metallofullerenes

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dc.contributor.author Garcia Borràs, Marc
dc.contributor.author Romero Rivera, Adrián
dc.contributor.author Osuna Oliveras, Sílvia
dc.contributor.author Luis Luis, Josep Maria
dc.contributor.author Swart, Marcel
dc.contributor.author Solà i Puig, Miquel
dc.date.issued 2012
dc.identifier.issn 1549-9626
dc.identifier.uri http://hdl.handle.net/10256/7128
dc.description.abstract Functionalization of endohedral metallofullerenes (EMFs) is an active line of research that is important for obtaining nanomaterials with unique properties that might be used in a variety of fields, ranging from molecular electronics to biomedical applications. Such functionalization is commonly achieved by means of cycloaddition reactions. The scarcity of both experimental and theoretical studies analyzing the exohedral regioselectivity of cycloaddition reactions involving EMFs translates into a poor understanding of the EMF reactivity. From a theoretical point of view, the main obstacle is the high computational cost associated with this kind of studies. To alleviate the situation, we propose an approach named the frozen cage model (FCM) based on single point energy calculations at the optimized geometries of the empty cage products. The FCM represents a fast and computationally inexpensive way to perform accurate qualitative predictions of the exohedral regioselectivity of cycloaddition reactions in EMFs. Analysis of the Dimroth approximation, the activation strain or distortion/interaction model, and the noncluster energies in the Diels–Alder cycloaddition of s-cis-1,3-butadiene to X@D3h-C78 (X = Ti2C2, Sc3N, and Y3N) EMFs provides a justification of the method
dc.description.sponsorship The following organizations are thanked for financial support: the Ministerio de Ciencia e Innovacion (MICINN, Project Nos. CTQ2011-25086/BQU and CTQ2011-23156), and the DIUE of the Generalitat de Catalunya (Project Nos. 2009SGR637 and 2009SGR528). MG.-B. thanks the Spanish MEC for doctoral fellowship AP2010-2517. S.O. is grateful to the European Community for postdoctoral fellowship PIOF-GA-2009-252856. Excellent service by the Centre de Serveis Cientific i Academics de Catalunya (CESCA) is gratefully acknowledged. The authors also are grateful to the computer resources, technical expertise, and assistance provided by the Barcelona Supercomputing Center-Centro Nacional de Supercomputation. Support for the research of M.S. was received through the ICREA Academia 2009 prize for excellence in research funded by the DIUE of the Generalitat de Catalunya
dc.format.mimetype application/pdf
dc.language.iso eng
dc.relation MICINN/PN 2012-2014/CTQ2011-25086
dc.relation MICINN/PN 2012-2014/CTQ2011-23156
dc.relation AGAUR/2009-2014/2009 SGR-637
dc.relation AGAUR/2009-2014/2009 SGR-528
dc.relation.isformatof Reproducció digital del document publicat a: http://dx.doi.org/10.1021/ct300044x
dc.relation.ispartof © Journal of Chemical Theory and Computation, 2012, vol. 8, núm. 5, p. 1671-1683
dc.relation.ispartofseries Articles publicats (D-Q)
dc.rights Tots els drets reservats
dc.subject Ful·lerens
dc.subject Fullerenes
dc.subject Enllaços químics
dc.subject Chemical bonds
dc.subject Reaccions químiques regioselectives
dc.subject Regioselectivity Chemical reactions
dc.title The Frozen Cage Model: A Computationally Low-Cost Tool for Predicting the Exohedral Regioselectivity of Cycloaddition Reactions Involving Endohedral Metallofullerenes
dc.type info:eu-repo/semantics/article
dc.rights.accessRights info:eu-repo/semantics/closedAccess
dc.relation.projectID info:eu-repo/grantAgreement/EC/FP7/252856
dc.type.version info:eu-repo/semantics/publishedVersion
dc.identifier.doi http://dx.doi.org/10.1021/ct300044x
dc.contributor.funder Ministerio de Ciencia e Innovación (Espanya)


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