Essential factors for control of the equilibrium in the reversible rearrangement of M3N@Ih-C80 fulleropyrrolidines: Exohedral functional groups versus endohedral metal clusters
dc.contributor.author
dc.date.accessioned
2015-04-30T10:18:51Z
dc.date.available
2015-04-30T10:18:51Z
dc.date.issued
2014-01-01
dc.identifier.issn
0947-6539
dc.identifier.uri
dc.description.abstract
The effects of exohedral moieties and endohedral metal clusters on the isomerization of M3N@Ih-C80 products from the Prato reaction through [1,5]-sigmatropic rearrangement were systematically investigated by using three types of fulleropyrrolidine derivatives and four different endohedral metal clusters. As a result, all types of derivatives provided the same ratios of the isomers for a given trimetallic nitride template (TNT) as the thermodynamic products, thus indicating that the size of the endohedral metal clusters inside C80 was the single essential factor in determining the equilibrium between the [6,6]-isomer (kinetic product) and the [5,6]-isomer. In all the derivatives, the [6,6]- and [5,6]-Prato adducts with larger metal clusters, such as Y3N and Gd3N, were equally stable, which is in good agreement with DFT calculations. The reaction rate of the rearrangement was dependent on both the substituent of exohedral functional groups and the endohedral metal-cluster size. Further DFT calculations and 13C NMR spectroscopic studies were employed to rationalize the equilibrium in the rearrangement between the [6,6]- and [5,6]-fulleropyrrolidines
dc.description.sponsorship
The authors are grateful to the computer resources, technical expertise, and assistance provided by the Barcelona Supercomputing Center (Centro Nacional de Supercomputacion) and technical assistance provided by the NMR service in the Laboratorium fur Organische Chemie in ETH. This study was supported in part by the Swiss National Foundation (200021 140451 (Y.Y.)); ETH Individual Investigator's Research Award (ETH-2511- 1 (Y.Y.)); PRESTO program from JST (Y.Y.); American Heart Association Researcher's Developing Grant (0930140N (Y.Y.)); Spanish MECD for a PhD fellowship (AP2010-2517 (M.G.B.)); Spanish MINECO for projects CTQ2011-23156/BQU, CTQ2011-25086/BQU, and Juan de la Cierva postdoctoral grant (JCI-2012-14438 (S.O.)); and the European Community for CIG project (PCIG14-GA-2013-630978 (S.O.)
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application/pdf
dc.language.iso
eng
dc.publisher
Elsevier
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/
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Reproducció digital del document publicat a: http://dx.doi.org/10.1002/chem.201403743
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© Chemistry - A European Journal, 2014, vol. 20, p. 14032-14039
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Articles publicats (D-Q)
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Tots els drets reservats
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dc.title
Essential factors for control of the equilibrium in the reversible rearrangement of M3N@Ih-C80 fulleropyrrolidines: Exohedral functional groups versus endohedral metal clusters
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/FP7/630978/EU/Computational Exploration of Directed Evolution rules for tuning enzymatic activities/DIREVENZYME
dc.type.version
info:eu-repo/semantics/publishedVersion
dc.identifier.doi
dc.identifier.idgrec
022143
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dc.relation.FundingProgramme
dc.relation.ProjectAcronym
dc.identifier.eissn
1521-3765