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Impact of C=C/B−N Replacement on the Diels–Alder Reactivity of Curved Polycyclic Aromatic Hydrocarbons
Author(s) -
GarcíaRodeja Yago,
Fernández Israel
Publication year - 2019
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.201901964
Subject(s) - cyclopentadiene , reactivity (psychology) , cycloaddition , corannulene , chemistry , diene , diels–alder reaction , computational chemistry , maleic anhydride , molecular orbital , density functional theory , aromaticity , photochemistry , fullerene , molecule , organic chemistry , catalysis , copolymer , polymer , medicine , natural rubber , alternative medicine , pathology
Abstract The influence of the replacement of C=C bonds by isoelectronic B−N moieties on the reactivity of π‐curved polycyclic aromatic hydrocarbons has been computationally explored by means of density functional theory calculations. To this end, we selected the Diels–Alder cycloaddition reactions of the parent corannulene and its BN‐doped counterparts with either cyclopentadiene or maleic anhydride. In addition, the analogous reactions involving larger buckybowls, such as BN‐hemifullerene, BN‐circumtrindene, and BN‐fullerene, have been also considered. It has been found that whereas corannulene behaves as a dienophile, its BN counterpart better acts as a diene. In contrast, the larger BN‐curved systems cannot be used as dienes in Diels–Alder reactions, but undergo facile (i.e., low barrier) cycloaddition reactions with cyclopentadiene. The observed trends in reactivity, which cannot be directly explained by using typical frontier molecular orbital arguments, are quantitatively described in detail by means of state‐of‐the‐art computational methods, namely the activation strain model of reactivity combined with the energy decomposition analysis method. The results of our calculations highlight the crucial role of the curvature of the system on the reactivity and its influence on the strength of the orbital interactions between the deformed reactants during their transformations.