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Reactivity and Selectivity of Bowl‐Shaped Polycyclic Aromatic Hydrocarbons: Relationship to C 60
Author(s) -
GarcíaRodeja Yago,
Solà Miquel,
Bickelhaupt F. Matthias,
Fernández Israel
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201502248
Subject(s) - reactivity (psychology) , selectivity , chemistry , polycyclic aromatic hydrocarbon , hydrocarbon , polycyclic compound , stereochemistry , organic chemistry , molecule , catalysis , medicine , alternative medicine , pathology
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 C 60 fullerene, which also produces the corresponding [6,6]‐cycloadduct exclusively. The behavior of the buckybowls considered herein resembles, in general, that of C 60 . 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.