title: Reactivity and Selectivity of Bowl-Shaped Polycyclic Aromatic Hydrocarbons: Relationship to C60.
abstract: The Diels-Alder reactivity of different bowl-shaped polycyclic aromatic hydrocarbons (namely, corannulene, cyclopentacorannulene, diindenochrysene, hemifullerene, and circumtrindene) has been explored computationally within the DFT framework. To this end, both the increase in reactivity with the size of the buckybowl and complete [6,6]-regioselectivity in the process have been analyzed in detail by using the activation strain model of reactivity in combination with the energy decomposition analysis method. These results have been compared with the parent C60 fullerene, which also produces the corresponding [6,6]-cycloadduct exclusively. The behavior of the buckybowls considered herein resembles, in general, that of C60 . Whereas the interaction energy between the deformed reactants along the reaction coordinate mainly controls the regioselectivity of the process, it is the interplay between the activation strain energy and the transition-state interaction that governs the reactivity of the system.
authors.affiliation: Departamento de Química Orgánica, Facultad de Química, Universidad Complutense, 28040, Madrid, Spain), Fax: (+34)913944310.
authors.forename: Yago
authors.identifier: http://orcid.org/0000-0001-6245-1665
authors.initials: Y
authors.lastname: García-Rodeja
authors.affiliation: Institut de Química Computacional and Departament de Química, Universitat de Girona, Campus Montilivi, 17071, Girona, Spain.
authors.forename: Miquel
authors.identifier: http://orcid.org/0000-0002-1917-7450
authors.initials: M
authors.lastname: Solà
authors.affiliation: Department of Theoretical Chemistry and Amsterdam, Center for Multiscale Modeling (ACMM), VU University, De Boelelaan 1083, 1081 HV, Amsterdam, The Netherlands.|Institute for Molecules and Materials (IMM), Radboud University Nijmegen, Heyendaalseweg 135, 6525 AJ, Nijmegen, The Netherlands.
authors.forename: F Matthias
authors.identifier: http://orcid.org/0000-0003-4655-7747
authors.initials: FM
authors.lastname: Bickelhaupt
authors.affiliation: Departamento de Química Orgánica, Facultad de Química, Universidad Complutense, 28040, Madrid, Spain), Fax: (+34)913944310. israel@quim.ucm.es.
authors.forename: Israel
authors.identifier: http://orcid.org/0000-0002-0186-9774
authors.initials: I
authors.lastname: Fernández
keywords: cycloaddition; density functional calculations; fullerenes; polyaromatic hydrocarbons; structure-activity relationships