Reactivity and Selectivity of Bowl‐Shaped Polycyclic Aromatic Hydrocarbons: Relationship to C60 |
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| Authors: | Yago García‐Rodeja Prof. Dr. Miquel Solà Prof. Dr. F. Matthias Bickelhaupt Dr. Israel Fernández |
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| Affiliation: | 1. Departamento de Química Orgánica, Facultad de Química, Universidad Complutense, Madrid, Spain), Fax: (+34)913944310;2. Institut de Química Computacional and Departament de Química, Universitat de Girona, Campus Montilivi, Girona, Spain;3. Department of Theoretical Chemistry and Amsterdam, Center for Multiscale Modeling (ACMM), VU University, Amsterdam, The Netherlands;4. Institute for Molecules and Materials (IMM), Radboud University Nijmegen, Nijmegen, The Netherlands |
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| 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. |
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| Keywords: | cycloaddition density functional calculations fullerenes polyaromatic hydrocarbons structure– activity relationships |
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