Simply put, Huckel's rule for aromaticity states
that a monocyclic system will be aromatic if there are 4n + 2 delocalised
electrons, (n an integer) contained within it. e.g.: 2, 6, 10, 14
etc.
Huckel arrived at this rule by performing molecular orbital calculations
on cyclic systems containing x carbon atoms, and with each carbon
atom supplying one pi electron. He connected high aromatic
stability with the presence of (4n + 2) electrons.
It is important to note that the number of carbon atoms in the
cyclic system, according to this rule, is irrelevant to the aromaticity
or otherwise of the molecule; it is purely based on the number of
delocalised electrons.
Not mentioned in the rule, but implicitly part of aromaticity is
the requirement that the ring is (almost or exactly) planar.
This is simply because the delocalisation only works when there
is significant overlap of the p orbitals (as mentioned earlier),
and any significant deviations from planarity will diminish the
p orbital overlap.
| Carbon atoms |
3 |
4 |
5 |
6 |
7 |
8 |
| Structure |
 |
 |
 |
 |
 |
 |
| pi electrons |
4n + 3 |
4n |
4n + 1 |
4n + 2 |
4n + 3 |
4n |
For example, let us consider cyclobutadiene briefly:
it has 4n electrons in the pi system, as we have seen. These
occupy energy levels as shown below:
| Cyclobutadiene |
Benzene |
 |
Cyclobutadiene has two bonding electrons, but it also
has two unpaired non-bonding electrons. These electrons do
not contribute to the stability of the molecule, and because they
are in high energy orbitals, they are available for reactions.
Benzene, on the other hand, has all 6 pi electrons
in bonding orbitals, and through this achieves extra stability.
|