A complete guide on the influence of metal clusters in the diels-alder regioselectivity of Ih-C80 endohedral metallofullerenes
dc.contributor.author
dc.date.accessioned
2015-03-24T16:33:55Z
dc.date.available
2015-03-24T16:33:55Z
dc.date.issued
2013-10-25
dc.identifier.issn
0947-6539
dc.identifier.uri
dc.description.abstract
The chemical functionalization of endohedral metallofullerenes (EMFs) has aroused considerable interest due to the possibility of synthesizing new species with potential applications in materials science and medicine. Experimental and theoretical studies on the reactivity of endohedral metallofullerenes are scarce. To improve our understanding of the endohedral metallofullerene reactivity, we have systematically studied with DFT methods the Diels-Alder cycloaddition between s-cis-1,3-butadiene and practically all X@I h-C80 EMFs synthesized to date: X=Sc3N, Lu 3N, Y3N, La2, Y3, Sc 3C2, Sc4C2, Sc3CH, Sc3NC, Sc4O2 and Sc4O3. We have studied both the thermodynamic and kinetic regioselectivity, taking into account the free rotation of the metallic cluster inside the fullerene. This systematic study has been made possible through the use of the frozen cage model (FCM), a computationally cheap approach to accurately predicting the exohedral regioselectivity of cycloaddition reactions in EMFs. Our results show that the EMFs are less reactive than the hollow Ih-C80 cage. Except for the Y3 cluster, the additions occur predominantly at the [5,6] bond. In many cases, however, a mixture of the two possible regioisomers is predicted. In general, [6,6] addition is favored in EMFs that have a larger charge transfer from the metal cluster to the cage or a voluminous metal cluster inside. The present guide represents the first complete and exhaustive investigation of the reactivity of Ih-C80-based EMFs
dc.description.sponsorship
We are grateful for financial support from the Spanish MICINN (projects CTQ2011-23156/BQU and CTQ2011-25086/BQU), the Catalan DIUE (projects 2009SGR637, 2009SGR528, and XRQTC), and the FEDER fund (grant UNGI08-4E-003). M.G.-B. thanks the Spanish MECD for a Ph. D. fellowship (AP2010-2517) and S.O. thanks the European Community for a postdoctoral fellowship (PIOF-GA-2009-252856). Excellent service by CESCA is acknowledged. The authors are also grateful to the computer resources and assistance provided by the BSC-CNS. M.S. thanks the Catalan DIUE for the ICREA Academia 2009 Award
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
Wiley-VCH Verlag
dc.relation
info:eu-repo/grantAgreement/MICINN//CTQ2011-23156/ES/AVANCES EN CATALISIS Y AROMATICIDAD/
info:eu-repo/grantAgreement/MICINN//CTQ2011-25086/ES/MODELIZACION MULTIESCALAR EN (BIO)QUIMICA/
AGAUR/2009-2014/2009 SGR-637
AGAUR/2009-2014/2009 SGR-528
dc.relation.isformatof
Reproducció digital del document publicat a: http://dx.doi.org/10.1002/chem.201302202
dc.relation.ispartof
© Chemistry - A European Journal, 2013, vol. 19, p. 14931-14940
dc.relation.ispartofseries
Articles publicats (D-Q)
dc.rights
Tots els drets reservats
dc.subject
dc.title
A complete guide on the influence of metal clusters in the diels-alder regioselectivity of Ih-C80 endohedral metallofullerenes
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/embargoedAccess
dc.embargo.terms
Cap
dc.date.embargoEndDate
info:eu-repo/date/embargoEnd/2026-01-01
dc.relation.projectID
info:eu-repo/grantAgreement/EC/FP7/252856/EU/Enzyme Design of Medical Interest/MEDENZYMEDESIGN
dc.type.version
info:eu-repo/semantics/publishedVersion
dc.identifier.doi
dc.identifier.idgrec
018351
dc.contributor.funder
dc.relation.FundingProgramme
dc.relation.ProjectAcronym
dc.identifier.eissn
1521-3765