Reaction Mechanism and Regioselectivity of the Bingel-Hirsch Addition of Dimethyl Bromomalonate to La@C2v-C82
dc.contributor.author
dc.date.accessioned
2016-05-03T07:21:03Z
dc.date.available
2016-05-03T07:21:03Z
dc.date.issued
2016-04-18
dc.identifier.issn
0947-6539
dc.identifier.uri
dc.description.abstract
We quantum chemically explore the thermodynamics and kinetics of all 65 possible mechanistic pathways of the Bingel-Hirsch addition of dimethyl bromomalonate to the endohedral metallofullerene La@C2v-C82 that result from the combination of 24 nonequivalent carbon atoms and 35 different bonds present in La@C2v-C82 by using dispersion-corrected DFT calculations. Experimentally, this reaction leads to four singly bonded derivatives and one fulleroid adduct. Of these five products, only the singly bonded derivative on C23 could be experimentally identified unambiguously. Our calculations show that La@C2v-C82 is not particularly regioselective under Bingel-Hirsch conditions. From the obtained results, however, it is possible to make a tentative assignment of the products observed experimentally. We propose that the observed fulleroid adduct results from the attack at bond 19 and that the singly bonded derivatives correspond to the C2, C19, C21, and C23 initial attacks. However, other possibilities cannot be ruled out completely. Fulleroid formation: Five experimentally observed but hitherto uncharacterized products in the Bingel-Hirsch (BH) addition of dimethyl bromomalonate to La@C2v-C82 were identified quantum chemically, only one of which is a fulleroid (see figure; white: C, dark red: La, green: Br, red: O, blue: H). Computational exploration also shows that the Bingel-Hirsch addition to La@C2v-C82 is not particularly regioselective, so at least ten products are expected, even under mild reaction conditions
dc.description.sponsorship
We thank the following organizations for financial support: the Spanish government (MINECO, project numbers CTQ2014-54306-P and CTQ2014-59212-P), the Generalitat de Catalunya (project number 2014SGR931 and Xarxa de Referència en Química Teòrica i Computacional), and the FEDER fund (European Fund for Regional Development) for the grant UNGI10-4E-801. We thank the National Research School Combination - Catalysis (NRSC-C), and The Netherlands Organization for Scientific Research (NWO/CW and NWO/EW). J.P.M. gratefully acknowledges a Ph.D. fellowship (register/application no. 217067/312543) from the Mexican National Council of Science and Technology (CONACYT). M.G.-B. thanks the Spanish MEC for a doctoral fellowship no. AP2010-2517. S.O. thanks the MINECO for the Juan de la Cierva fellowship and the European Community for the CIG project (FP7-PEOPLE-2013-CIG-630978)
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
Wiley-VCH Verlag
dc.relation
info:eu-repo/grantAgreement/MINECO//CTQ2014-54306-P/ES/ESTUDIOS TEORICO-EXPERIMENTALES DE CICLACIONES CATALIZADAS POR METALES DE TRANSICION. NUEVOS DESARROLLOS EN AROMATICIDAD, FUNCIONALES DE LA DENSIDAD Y QUIMICA SUPRAMOLECULAR/
info:eu-repo/grantAgreement/MINECO//CTQ2014-59212-P/ES/SPIN STATE AND ENZYMATIC CATALYSIS BASED ON BOTTOM-UP COMPUTATIONAL DESIGN/
AGAUR/2014-2016/2014 SGR-931
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Versió postprint del document publicat a: http://dx.doi.org/10.1002/chem.201504668
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© Chemistry - A European Journal, 2016, vol. 22, núm. 17, p. 5953-5962
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Articles publicats (D-Q)
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Tots els drets reservats
dc.subject
dc.title
Reaction Mechanism and Regioselectivity of the Bingel-Hirsch Addition of Dimethyl Bromomalonate to La@C2v-C82
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/openAccess
dc.embargo.terms
Cap
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/acceptedVersion
dc.identifier.doi
dc.identifier.idgrec
024634
dc.contributor.funder
dc.type.peerreviewed
peer-reviewed
dc.relation.FundingProgramme
dc.relation.ProjectAcronym
dc.identifier.eissn
1521-3765