How to Determine the Aromaticity of a Ring System

By Arthur Winter

You can determine whether a ring system is aromatic, anti-aromatic, or non-aromatic by determining whether it meets certain conditions. To be aromatic, a molecule must meet the following four conditions:

  • It must be a ring.

  • It must be flat (planar).

  • It must have in each atom of the ring a p orbital that’s orthogonal to the plane of the ring. In other words, no atom in the ring can be sp3 hybridized.

  • It must have a Hückel number of pi electrons, following the 4n + 2 rule.

If the molecule meets the first three conditions, but only has 4n pi electrons, the molecule is anti-aromatic. If the molecule fails any or all of the first three conditions, then the molecule is non-aromatic. Following are some details about each of these points.

The first condition is that only rings can be aromatic. Acyclic systems cannot be aromatic.

The second condition involves the shape of the ring. Ringed systems can be flat or three-dimensional. Most conjugated ring systems are flat in order to maximize the overlap between the p orbitals. But some exceptions exist. Cyclodecapentaene, for example, shown in the figure, is puckered because two hydrogens in the ring are pushed into each other’s space, and the ring is forced out of planarity so that the hydrogens can occupy separate spaces. Because of its nonplanar structure, cyclodecapentaene is non-aromatic. Removing the two hydrogens and replacing them with a carbon bond to make naphthalene erases this problem; naphthalene is planar (and aromatic).

image0.jpg

Cyclooctatetraene (shown in the next figure) is another example of a molecule that has alternating double bonds around the ring but isn’t planar. Instead, this ring system adopts a puckered tub-shaped conformation. Why? Because if it remained flat, it would become anti-aromatic as a result of having a non-Hückel number of pi electrons (8)! Because anti-aromatic systems are so unstable, this compound puckers and sacrifices the p orbital overlap so that it won’t have to endure the instability associated with being anti-aromatic.

image1.jpg

The third condition involves the orbitals. Aromatic systems must have an unbroken ring of p orbitals, so any ring that contains an sp3 hybridized carbon will not be aromatic. Cycloheptatriene, shown in the next figure, is non-aromatic because one of the ring carbons is sp3 hybridized. However, carbocations (positively charged carbons) are sp2 hybridized (and have an empty p orbital), so the cycloheptatriene cation has an unbroken ring of p orbitals and is an aromatic compound.

image2.jpg

Finally, to be aromatic, a ring must have a Hückel number of electrons (4n + 2). The table gives solutions to these equations for low values of n.

Pi Electron Counts
Integer (n) Aromatic Numbers (4n + 2) Anti-aromatic Numbers (4n)
0 2
1 6 4
2 10 8
3 14 12
4 18 16