title: Reaction Mechanism and Regioselectivity of the Bingel-Hirsch Addition of Dimethyl Bromomalonate to La@C2v -C82.
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.
authors.affiliation: Institut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona, Campus de Montilivi, 17071, Girona, Catalonia, Spain.
authors.forename: Juan Pablo
authors.initials: JP
authors.lastname: Martínez
authors.affiliation: Institut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona, Campus de Montilivi, 17071, Girona, Catalonia, Spain.
authors.forename: Marc
authors.identifier: http://orcid.org/0000-0001-9458-1114
authors.initials: M
authors.lastname: Garcia-Borràs
authors.affiliation: Institut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona, Campus de Montilivi, 17071, Girona, Catalonia, Spain.
authors.forename: Sílvia
authors.identifier: http://orcid.org/0000-0003-3657-6469
authors.initials: S
authors.lastname: Osuna
authors.affiliation: Department of Theoretical Chemistry and Amsterdam Center for Multiscale Modeling, Vrije Universiteit Amsterdam, De Boeleaan 1083, 1081 HV, Amsterdam, The Netherlands.|Departament de Química Orgànica & IQTCUB, Universitat de Barcelona, Martí i Franquès 1-11, 08028, Barcelona, Catalonia, Spain.|Institució Catalana de Recerca i Estudis Avançats (ICREA), Pg. Lluís Companys 23, 08010, Barcelona, Catalonia, Spain.
authors.forename: Jordi
authors.identifier: http://orcid.org/0000-0002-0814-5074
authors.initials: J
authors.lastname: Poater
authors.affiliation: Department of Theoretical Chemistry and Amsterdam Center for Multiscale Modeling, Vrije Universiteit Amsterdam, De Boeleaan 1083, 1081 HV, Amsterdam, The Netherlands. F.M.Bickelhaupt@vu.nl.|Radboud University Nijmegen, Institute for Molecules and Materials, Heyendaalseweg 135, 6525 AJ, Nijmegen, The Netherlands. F.M.Bickelhaupt@vu.nl.
authors.forename: F Matthias
authors.identifier: http://orcid.org/0000-0003-4655-7747
authors.initials: FM
authors.lastname: Bickelhaupt
authors.affiliation: Institut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona, Campus de Montilivi, 17071, Girona, Catalonia, Spain. Miquel.Sola@udg.edu.
authors.forename: Miquel
authors.identifier: http://orcid.org/0000-0002-1917-7450
authors.initials: M
authors.lastname: Solà
keywords: Bingel-Hirsch reaction; La@C2v-C82; density functional calculations; endohedral metallofullerenes; fullerenes; reaction mechanisms; regioselectivity