17.9 : Aromatic Hydrocarbon Anions: Structural Overview

Neutral hydrocarbons like cyclopentadiene with an odd number of carbon atoms and one intervening CH₂ group in the ring are not aromatic. Cyclopentadiene with 4 π electrons does not satisfy the 4n + 2 π electron rule. Additionally, the intervening CH₂ group is sp³ hybridized and lacks a vacant p orbital, thereby interrupting the overlap of p orbitals in a continuous manner and preventing the delocalization of π electrons throughout the ring.

Due to the absence of continuous overlap of p orbitals, cyclopentadiene does not comply with aromaticity criteria. However, the removal of one hydrogen with both or one or no electrons from the CH₂ group drives the conversion of sp³ carbon to sp², thereby converting cyclopentadiene into cyclopentadienyl cation, radical, and anion, respectively, having a vacant p orbital. Among all the three species, cyclopentadienyl cation and radical with four and five π electrons, respectively, do not meet the criteria of 4n + 2 π electrons and are not aromatic. On the other hand, cyclopentadienyl anion with 6 π electrons, a continuous overlapping ring of p orbitals, and delocalized π electron density becomes aromatic. The electrostatic potential map of the anion corroborates the delocalization of π electrons throughout the ring. Moreover, the five resonance structures of cyclopentadienyl anion and the occupancy of bonding molecular orbitals by all 6 π electrons in the frost diagram validate the unusual stability of the anion.