And antiaromaticity

The special case of pericyclic reactions is an appropriate means of introducing the subject These reactions are very common, and were extensively studied experimentally and theoretically. They also provide a direct and straightforward connection with aromaticity and antiaromaticity, concepts that mm out to be quite useful in analyzing phase changes in chemical reactions. 

The results of the derivation (which is reproduced in Appendix A) are summarized in Figure 7. This figure applies to both reactive and resonance stabilized (such as benzene) systems. The compounds A and B are the reactant and product in a pericyclic reaction, or the two equivalent Kekule structures in an aromatic system. The parameter t, is the reaction coordinate in a pericyclic reaction or the coordinate interchanging two Kekule structures in aromatic (and antiaromatic) systems. The avoided crossing model [26-28] predicts that the two eigenfunctions of the two-state system may be fomred by in-phase and out-of-phase combinations of the noninteracting basic states A) and B). State A) differs from B) by the spin-pairing scheme. 

Ring Currents Aromatic and Antiaromatic Magnetic Resonance Imaging Spectra by the Thousands Gas Chromatography GC/MS and MS/MS... 

Ring Currents Aromatic and Antiaromatic Spectra by the Thousands... 

The Hiickel rule predicts aromaticity for the six-7c-electron cation derived from cycloheptatriene by hydride abstraction and antiaromaticity for the planar eight-rc-electron anion that would be formed by deprotonation. The cation is indeed very stable, with a P Cr+ of -1-4.7. ° Salts containing the cation can be isolated as a product of a variety of preparative procedures. On the other hand, the pK of cycloheptatriene has been estimated at 36. ° This value is similar to those of normal 1,4-dienes and does not indicate strong destabilization. Thus, the seven-membered eight-rc-electron anion is probably nonplanar. This would be similar to the situation in the nonplanar eight-rc-electron hydrocarbon, cyclooctatetraene. 

Tlie tautomerism of heteroaromatic compounds is intimately related to the problem of aromaticity and antiaromaticity (87MI1,94MI1), this being especially true for the compounds of this chapter, which are borderline between these showing Fliickel behavior and polyenic compounds (nonaromatic). 

It is known that unsaturated three-membered nitrogen heterocycles display tautomerism involving nonaromatic and antiaromatic (i.e., Air systems) forms. In all cases, the nonantiaromatic tautomer is the most stable 1-azirine la and 1-diazirine 2a. Nonetheless, antiaromatic tautomers are known, for instance, triazirines 3. 

Although five equivalent resonance structures can be drawn for all three species, Huckel s rule predicts that only the six-ir-electron anion should be aromatic. The four-77-electron cyciopentadienyl carbocation and the five-7r-electron cyciopentadienyl radical are predicted to be unstable and antiaromatic. 

The thiirene oxide system is of particular interest due to it being simultaneously both a potentially nonbenzenoid aromatic (4n + 2)n and antiaromatic 4nn Hiickel system. 

Minkin VI, Clukhoytsev MN, Simkin BY (1994) Aromaticity and Antiaromaticity, Electronic and Structural Aspects. Wiley, New York... 

Using the nomenclature of Dewar and Zimmerman, the transition state for the 2, + 2S cycloaddition is a 4n Hiickel system (zero nodes) and is antiaromatic in the ground state and aromatic in the excited state. The transition state for the 2S + 20 cycloaddition is a 4n Mobius system (one node) and is aromatic in the ground state and antiaromatic in the excited state (see Chapter 8). The general cycloaddition rules are given in Table 9.5. 

Ronald Breslow (Co-Chair) is University Professor of Chemistry, Columbia University, and a founder of a new pharmaceutical company. He received his B.A. (1952), M.A. (1954), and Ph.D. (1955) from Harvard University. His research area is organic chemistry with specialization in biochemical model systems, biomimetic synthetic methods, reaction mechanisms, and aromaticity and antiaromaticity. He served as president of the American Chemical Society in 1996 and has authored a book for the general public, Chemistry Today and Tomorrow The Central, Useful, and Creative Science. He is a member of the National Academy of Sciences, the American Academy of Arts and Sciences, and the American Philosophical Society. He received the U.S. National Medal of Science in 1991. 

Figure 7. Aromatic and antiaromatic systems in the ground state (GS) and the twin excited state (ES). The parameter E, is the coordinate that transforms A to B.

The second mechanism, due to the permutational properties of the electronic wave function is referred to as the permutational mechanism. It was introduced in Section I for the H4 system, and above for pericyclic reactions and is closely related to the aromaticity of the reaction. Following Evans principle, an aromatic transition state is defined in analogy with the hybrid of the two Kekule structures of benzene. A cyclic transition state in pericyclic reactions is defined as aromatic or antiaromatic according to whether it is more stable or less stable than the open chain analogue, respectively. In [32], it was assumed that the in-phase combination in Eq. (14) lies always the on the ground state potential. As discussed above, it can be shown that the ground state of aromatic systems is always represented by the in-phase combination of Eq. (14), and antiaromatic ones—by the out-of-phase combination. 

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