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An Energetic Measure of Aromaticity and Antiaromaticity Based on the Pauling-Wheland Resonance Energies
Various criteria based on geometric, energetic, magnetic, and electronic properties are employed to delineate aromatic and antiaromatic systems. The recently proposed block‐localized wave function (BLW) method evaluates the original Pauling–Wheland adiabatic resonance energy (ARE), defined as the en...
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| Published in: | Chemistry : a European journal 2006-02, Vol.12 (7), p.2009-2020 |
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| Main Authors: | , |
| Format: | Article |
| Language: | English |
| Subjects: | |
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| Online Access: | Get full text |
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| Summary: | Various criteria based on geometric, energetic, magnetic, and electronic properties are employed to delineate aromatic and antiaromatic systems. The recently proposed block‐localized wave function (BLW) method evaluates the original Pauling–Wheland adiabatic resonance energy (ARE), defined as the energy difference between the real conjugated system and the corresponding virtual most stable resonance structure. The BLW‐derived ARE of benzene is 57.5 kcal mol−1 with the 6‐311+G** basis set. Kistiakowsky's historical experimental evaluation of the stabilization energy of benzene (36 kcal mol−1), based on heats of hydrogenation, seriously underestimates this quantity due to the neglect of the partially counterbalancing hyperconjugative stabilization of cyclohexene, employed as the reference olefin (three times) in Kistiakowsky's evaluation. Based instead on the bond‐separation‐energy reaction involving ethene, which has no hyperconjugation, as well as methane and ethane, the experimental resonance energy of benzene is found to be 65.0 kcal mol−1. We derived the “extra cyclic resonance energy” (ECRE) to characterize and measure the extra stabilization (aromaticity) of conjugated rings. ECRE is the difference between the AREs of a fully cyclically conjugated compound and an appropriate model with corresponding, but interrupted (acyclic) conjugation. Based on 1,3,5‐hexatriene, which also has three double bonds, the ECRE of benzene is 36.7 kcal mol−1, whereas based on 1,3,5,7‐octatetraene, which has three diene conjugations, the ECRE of benzene is 25.7 kcal mol−1. Computations on a series of aromatic, nonaromatic, and antiaromatic five‐membered rings validate the BLW‐computed resonance energies (ARE). ECRE data on the five‐membered rings (derived from comparisons with acyclic models) correlate well with nucleus‐independent chemical shift (NICS) and other quantitative aromaticity criteria. The ARE of cyclobutadiene is almost the same as butadiene but is 10.5 kcal mol−1 less than 1,3,5‐hexatriene, which also has two diene conjugations. The instability and high reactivity of cyclobutadiene thus mainly result from the σ‐frame strain and the π–π Pauli repulsion.
Measuring stability: The Pauling–Wheland adiabatic resonance energy (the energy difference between the real conjugated system and the corresponding virtual most stable resonance structure, see scheme) has been computed based on a valence‐bond‐like method for various aromatic and antiaromatic systems. |
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| ISSN: | 0947-6539 1521-3765 |
| DOI: | 10.1002/chem.200500376 |