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Reaction Mechanism and Regioselectivity of the Bingel-Hirsch Addition of Dimethyl Bromomalonate to La@C2v-C82

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

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)

Wiley-VCH Verlag

Manager: Ministerio de Economía y Competitividad (Espanya)
Generalitat de Catalunya. Agència de Gestió d’Ajuts Universitaris i de Recerca
Author: Martínez, Juan Pablo
Garcia Borràs, Marc
Osuna Oliveras, Sílvia
Poater i Teixidor, Jordi
Bickelhaupt, F. Matthias
Solà i Puig, Miquel
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
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)
Document access: http://hdl.handle.net/2072/297702
Language: eng
Publisher: Wiley-VCH Verlag
Rights: Tots els drets reservats
Subject: Reaccions químiques
Chemical reactions
Funcional de densitat, Teoria del
Density functionals
Bingel-Hirsch, Reacció de
Bingel-Hirsch reaction
Fullerenes
Ful·lerens
Title: Reaction Mechanism and Regioselectivity of the Bingel-Hirsch Addition of Dimethyl Bromomalonate to La@C2v-C82
Type: info:eu-repo/semantics/article
Repository: Recercat

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