Aromatic Ions

In order to be aromatic, a molecule must be cyclic and planar and must also have an
uninterrupted cyclic π electron cloud. In addition, it must fulfill Hückel's rule (4n +
2 π electrons). However, the number of p orbitals that participate in the π system do
not need to be equal to the number of π electrons. Thus, anions, cations, and radicals
may be aromatic too and Hückel's rule may also be applied to them accordingly.

Due to the sp3-hybridized ring carbon, cyclopentadiene (pKa= 16) is not aromatic,
as it does not possess an uninterrupted cyclic π electron cloud.

 If a hydride anion (H−) is removed from the sp3-hybridized ring carbon,

the cyclopentadienyl cation is formed, and the hybridization of the sp3-hybridized
ring carbon is altered to sp2. Consequently, the cyclic cyclopentadienyl cation is
planar and it possesses a cyclic uninterrupted π electron cloud. However, it does not
meet Hückel's rule, as it has 4 π electrons. Therefore, it is antiaromatic.
 Abstraction of a hydrogen atom from the sp3-hybridized ring carbon yields
the cyclopentadienyl radical. The hybridization of the sp3-hybridized ring carbon
is transformed to sp2, as well. Analogous to the cyclopentadienyl cation, the
cyclopentadienyl radical does not meet Hückel's rule, as it possesses five π electrons.
Thus, it is not aromatic.
 The abstraction of a proton (H+) from the sp3-hybridized ring carbon yields
the cyclopentadienyl anion. The hybridization of the sp3-hybridized ring carbon is
consequently altered to sp2, as well. The cyclic cyclopentadienyl anion is planar, it
possesses a cyclic uninterrupted π electron cloud, and it meets Hückel's rule, as it has
4*1 + 2 (n = 1) π electrons. Therefore, the cyclopentadienyl anion is a relatively
stable aromatic species. As a result, the acidity of cyclopentadiene may be compared
to that of water (pKa= 16). In contrast to the cyclopentadienyl cation and the radical,
it can easily be obtained through treatment with a base. The cyclopentadienyl cation
and radical are considerably instable and reactive species.