Journal
PURE AND APPLIED CHEMISTRY
Volume 86, Issue 5, Pages 747-753Publisher
WALTER DE GRUYTER GMBH
DOI: 10.1515/pac-2013-1212
Keywords
aromatic compounds; bowl inversion; buckybowls; NMS-IX; organic chemistry; polycyclic aromatics
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Funding
- Grants-in-Aid for Scientific Research [26288020, 25410124] Funding Source: KAKEN
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The correlation between the bowl-inversion energy and the bowl depth for sumanenes monosubstituted with an iodo, formyl, or nitro group was investigated experimentally and by theoretical calculations. The bowl-inversion energies of the substituted sumanenes were determined experimentally by two-dimensional NMR exchange spectroscopy measurements. Various density functional theory methods were examined for the calculation of the structure and the bowl-inversion energy of sumanene, and it was found that PBE0, omega B97XD, and M06-2X gave better fits of the experimental value than did B3LYP. The experimental value was well reproduced at these levels of theory. The bowl structures and bowl-inversion energies of monosubstituted sumanenes were therefore calculated at the omega B97XD/6-311+ G(d, p) level of theory. In both the experiments and the calculations, the correlation followed the equation Delta E = acos(4)theta, where a is a coefficient, Delta E is the bowl-inversion energy, and cos theta is the normalized bowl depth, indicating that the bowl inversion follows a double-well potential energy diagram.
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