Pros and cons of σ -aromaticity

A discussion of σ-aromaticity requires a distinction between σ-conjugation, σ-electron delocalization, and σ-bond delocalization, all of which can be considered as prerequisites of σ-aromatic character. All molecules with three or more atoms encounter σ-conjugative interactions. Also, all σ-electrons are delocalized if the term delocalization is taken in its quantum theoretical meaning. However, σ-conjugation and σ-electron delocalization do not necessarily imply σ-bond delocalization. - One can distinguish between three different modes of σ-delocalization: ribbon delocalization in acyclic molecules and larger rings, surface delocalization in small rings, and volume delocalization in cage compounds. Surface delocalization of σ-electrons is found to lead to σ-bond delocalization. An example is cyclopropane. Bonding in cyclopropane can only be described in terms of nonclassical 2-electron 3-center and 4-electron 3-center bonds. Application of the criteria used to define π-aromaticity reveals that the properties of cyclopropane are in line with these criteria and that the term σ-aromaticity cannot be rejected on the grounds that aromaticity is restricted to π-electrons. The pros and cons of using the term σ-aromaticity in chemical discussions are presented.

Английский

Tetrahedron. – 1988. – Vol. 44, № 24. – P. 7427–7454.