title: The Regioselectivity of Bingel-Hirsch Cycloadditions on Isolated Pentagon Rule Endohedral Metallofullerenes.
abstract: In this work, the Bingel-Hirsch addition of diethylbromomalonate to all non-equivalent bonds of Sc3N@D3h -C78 was studied using density functional theory calculations. The regioselectivities observed computationally allowed the proposal of a set of rules, the predictive aromaticity criteria (PAC), to identify the most reactive bonds of a given endohedral metallofullerene based on a simple evaluation of the cage structure. The predictions based on the PAC are fully confirmed by both the computational and experimental exploration of the Bingel-Hirsch reaction of Sc3N@D5h -C80, thus indicating that these rules are rather general and applicable to other isolated pentagon rule endohedral metallofullerenes.
authors.affiliation: Institut de Química Computacional i Catàlisi (IQCC), Departament de Química, Universitat de Girona, Campus 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: Department of Chemistry, University of Texas at El Paso, El Paso, Texas, 79968, USA.
authors.forename: Maira R
authors.identifier: http://orcid.org/0000-0002-5151-0479
authors.initials: MR
authors.lastname: Cerón
authors.affiliation: Institut de Química Computacional i Catàlisi (IQCC), Departament de Química, Universitat de Girona, Campus Montilivi, 17071, Girona, Catalonia, Spain. silvia.osuna@udg.edu.
authors.forename: Sílvia
authors.initials: S
authors.lastname: Osuna
authors.affiliation: Department of Chemistry, University of Texas at El Paso, El Paso, Texas, 79968, USA.
authors.forename: Marta
authors.identifier: http://orcid.org/0000-0003-2696-4230
authors.initials: M
authors.lastname: Izquierdo
authors.affiliation: Institut de Química Computacional i Catàlisi (IQCC), Departament de Química, Universitat de Girona, Campus Montilivi, 17071, Girona, Catalonia, Spain. josepm.luis@udg.edu.
authors.forename: Josep M
authors.identifier: http://orcid.org/0000-0002-2880-8680
authors.initials: JM
authors.lastname: Luis
authors.affiliation: Department of Chemistry, University of Texas at El Paso, El Paso, Texas, 79968, USA. echegoyen@utep.edu.
authors.forename: Luis
authors.initials: L
authors.lastname: Echegoyen
authors.affiliation: Institut de Química Computacional i Catàlisi (IQCC), Departament de Química, Universitat de Girona, Campus 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: aromaticity; cage compounds; density-functional calculations; fullerenes; supramolecular chemistry