Ace Your Next Organic Chemistry Exam.: Aromaticity

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Aromaticity
By James Ashenhurst
Frost Circles
Last updated: April 15th, 2020 |
We’ve spent a lot of time in previous posts “building up” and drawing out the molecular
orbitals for various species. In this post we’ll learn an extremely useful shortcut that will help
us draw the energy levels of cyclic pi-systems extremely quickly.

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The trick is called “Frost Circles”, or, sometimes, the “Polygon method”.
Table ofMaster
Contents
Organic
The Molecular Orbitals Of Benzene Can Be Superimposed On A Hexagon With the
Chemistry

Vertex Pointing Down


 Previous 
The Molecular Orbitals Of Cyclobutadiene Can Be Superimposed On A Square With the
Vertex Pointing Down
Frost Circles (The Polygon Method): A Useful Mnemonic For Drawing Energy Levels In
Cyclic Pi Systems
Frost Circles For Three-Membered Rings
Frost Circles For Four-Membered Rings
Frost Circles For Five-Membered Rings
Six-Membered Rings
Seven-Membered Rings
Eight-Membered Rings
Summary: Frost Circles
Notes
(Advanced) References and Further Reading

1. The Molecular Orbitals Of Benzene Can Be Superimposed On A


Hexagon With the Vertex Pointing Down
First:  Recall that we saw the energy levels of the molecular orbitals of benzene look like this:

Useful observation: these energy levels can be superimposed on a hexagon with the
vertex pointing down. Like this!

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Let’s do another one.


2. The Molecular Orbitals Of Cyclobutadiene Can Be Superimposed
On A Square With the Vertex Pointing Down
We’ve seen what the molecular orbitals for cyclobutadiene look like; the two highest energy
levels are each singly occupied (and non-bonding, to boot) which helps to explain why
cyclobutadiene is so spectacularly unstable.
The energy levels for cyclobutadiene can be superimposed on a diamond, which is just a
fancy name for a square with its vertex pointing down.

That’s pretty cool. You might wonder…. does it work for other polygons too?
3. Frost Circles (The Polygon Method): A Useful Mnemonic For Drawing
Energy Levels In Cyclic Pi Systems
Indeed it does. Back in 1953, Frost published an article describing this method for drawing
out the energy levels in cyclic systems, with a simplified version as follows [note]
“A circle… is inscribed with a polygon with one vertex pointing down; the vertices
represent energy levels with the appropriate energies”. 
Vertices below the halfway mark of the circle are considered bonding orbitals, and vertices
above the halfway mark are considered antibonding orbitals. If vertices are exactly in the
middle (as they are for 4- and 8- membered rings) they represent non-bonding orbitals.

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This idea is presented in the diagram below for 3, 4, 5, 6, 7, and 8-membered rings:
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This is an extremely useful mnemonic! This saves us a lot of work in building energy levels
from the ground up.
To draw the molecular orbitals of a cyclic pi system, all we have to do is draw the appropriate
polygon, vertex-down, and then fill it up with electrons.
Let’s see how we can apply these “Frost Circles”  for 3, 4, 5, 6, 7, and 8 membered rings.
(Although we’re going to skip drawing the actual circles, and just focus on the positions of the
orbitals).
4. Frost Circles For Three-Membered Rings
There are two important configurations of energy levels for 3-membered cyclic pi systems,
depending on the number of pi electrons.
With two pi electrons, we’d expect an aromatic molecule.  One example is the
cyclopropenium cation (below left), which is indeed aromatic.
With 4 pi electrons, an antiaromatic molecule is expected.  Oxirene (below right) which has
never been isolated,  is in this category.

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5. Frost Circles For Four-Membered Rings


Cyclobutadiene was covered above, and in the last post. Note that the molecular orbital
diagram predicts that if you rip o two of the pi-electrons, the resulting cyclobutene di-
cation should be aromatic,  (Substituted cyclobutene dications have indeed been
synthesized and found to be aromatic, by the group of the estimable, late, George
Olah) [note]
6. Frost Circles For Five-Membered Rings
Cyclic 5-membered pi systems with 6 pi electrons are predicted to be aromatic. Examples are
abundant. such as the cyclopentadienyl anion (below left), furan (below right), pyrrole,
thiophene, imidazole, and many others. And yes, arsoles are aromatic too, but you probably
didn’t need me to tell you that.

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Although not drawn here, removing 2 pi electrons would result in an antiaromatic system. The
cyclopentadienyl cation is a classic example.
7. Six-Membered Rings
Already covered above – but note that the rules can be applied not only for benzene, but also
“heterocycles” (i.e. aromatic rings with at least one non-carbon ring atom) such as pyridine,
pyrimidine, and even the “pyrylium cation”.

8. Seven-Membered Rings
Cyclic 7-membered pi systems with 6 pi electrons are predicted to be aromatic.
For a ring entirely comprised of carbon atoms, this corresponds to the cycloheptatrienyl
cation (sometimes known as the “tropylium ion”).
We’re used to thinking of carbocations as being unstable intermediates with a short lifetime.
But the aromatic tropylium ion is such a stable salt you can actually put it in a bottle. Aldrich
sells it.
The Frost circle method gives us the energy levels for the tropylium ion:

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9. Eight-Membered Rings
With 8 pi electrons, cyclooctatetraene is predicted to be antiaromatic, and its molecular
orbitals are predicted to look like this:

If you read the earlier post on antiaromaticity, however, you’ll recall that cyclooctatetraene
can “escape” from antiaromaticity by adopting a tub-like shape. The molecular orbital levels
we’d predict from the polygon method thus do not exactly correspond to the actual energy
levels of cyclooctatetraene itself – it’s not a diradical, for instance.
That’s not quite the end of the story, however. Just like anti aromatic cyclobutadiene can be
made aromatic through the removal of two electrons, the stability of (theoretically
antiaromatic) cyclooctatetraene can likewise be adjusted by the removal or addition of two
pi-electrons to give 6 or 10 pi-electrons, respectively.

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Chemical relatives (“derivatives”) of the cyclooctatetraene dication (6 pi electrons) and the


cyclooctatetraene dianion (10 pi electrons) have been synthesized and found to have
aromatic character.
Therefore we would predict that these molecules are planar, unlike cyclooctatetraene itself.
[In fact, this has been confirmed for the cyclooctatetraene dianion by X-ray crystallography
– reference]
10. Summary: Frost Circles
While there’s no end of interesting things to learn about aromaticity (homoaromaticity,
anyone?) this post concludes our treatment of it for the time being.
In the next series of articles we’ll finally get in to discussing the reactions of aromatic
compounds, beginning with the most important reaction type of all: electrophilic aromatic
substitution.
Many thanks to Matt Knowe for assistance with this article. 
 

Notes
[Note 1]  The more complex version is:
 A circle centered at α with radius 2β is inscribed with a polygon with one vertex
pointing down; the vertices represent energy levels with the appropriate energies

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What are these terms “α” and “2β”, you may ask? The answer is beyond the scope of what
we’ll discuss here, but the essence is that they are important terms in Hückel Molecular
OrbitalMaster
Method, a way of simplifying the Schrödinger Wave Equation for pi systems by
treatingChemistry
the pi electrons and sigma electrons separately.  It’s a powerful and useful method
Organic

for calculating the energies of pi systems and understanding their reactions.


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[Note 2] The stability arising from aromaticity in the cyclobutadiene dication should be
reduced considerably, however, by the Coulombic repulsion arising from the di-cationic
nature of the molecule (like charges repel, after all). Similarly, the stability arising from
aromaticity of the cyclooctatetraene dianion is lessened somewhat by the repulsion of its two
negative charges.

(Advanced) References and Further Reading


Synthesis and Isolation of cyclooctatetraene dianion:
THE CYCLOÖCTATETRAENYL DIANION
Thomas J. Katz
Journal of the American Chemical Society 1960 82 (14), 3784-3785
DOI: 10.1021/ja01499a077
In this paper Prof. Thomas Katz of Columbia University shows how the
cyclooctatetraene dianion can be prepared by reducing cyclooctatetraene with two
equivalents of potassium metal.
Structure of the 10.pi. electron cyclooctatetraene dianion in potassium diglyme 1,3,5,7-
tetramethylcyclooctatetraene dianion, [K((CH3OCH2CH2)2O)]2[C8H4(CH3)4]
Stephen Z. Goldberg, Kenneth N. Raymond, C. A. Harmon, and David H. Templeton
Journal of the American Chemical Society 1974 96 (5), 1348-1351
DOI: 10.1021/ja00812a015
This 1974 work has the first published crystal structure of the cyclooctatetraene dianion
and show that it is indeed planar and has structural features consistent with
aromaticity.
Free Cyclooctatetraene Dianion: Planarity, Aromaticity, and Theoretical Challenges
Alexander Yu. Sokolov, D. Brandon Magers, Judy I. Wu, Wesley D. Allen, Paul v. R.
Schleyer, and Henry F. Schaefer, III
Journal of Chemical Theory and Computation 2013 9 (10), 4436-4443
DOI: 10.1021/ct400642y 
So is cyclooctatetraene actually aromatic? This paper suggests that while the
cyclooctatetraene dianion has considerable resonance stabilization (25 kcal/mol, vs.
about 33 kcal/mol for benzene) this stabilization is swamped by Coulombic repulsion of
the anions, and as noted by commenter Frosty the Circle, : “Like many multiply
charged anions, COT2− exists in isolation only… as a short-lived resonance state lying
above neutral COT” “….Charge-compensating complexation of COT2−with two sodium
cations results in a thermodynamically stable Na2COT compound”

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Comments

Organic
February 25, 2018 at 12:20 pm
How to make molecular orbital energy level of non-cyclic organic
compounds?? Is there any perfect method for all compounds??
Please describe
Reply
James Ashenhurst
April 9, 2019 at 12:27 pm
If we’re strictly discussing pi systems, I suggest looking here:
https://www.masterorganicchemistry.com/2017/02/16/molec

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ular-orbitals-of-the-allyl-cation-allyl-radical-and-allyl-
anion/
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Dipita karmakar
February 21, 2019 at 8:02 am
Is cyclobutadienyl anion aromatic or not
Reply
James Ashenhurst
April 9, 2019 at 12:29 pm
Cyclobutadienyl di-anion, yes, because it would have six pi
electrons. Cyclobutadienyl anion, no, because it can only be
formed from deprotonation of C-H and the negative charge
(and ensuing lone pair) would be at right angles to the pi
system.
Reply

Frosty the Circle


September 18, 2019 at 8:02 am
Your diagram of the cyclooctatetraene dianion shows the added
electrons in a non-bonding orbital. With 10 electrons it would obey
the numerology of Huckel’s rule but the diagram argues against it
with the added electrons in the non-bonding orbitals.
The compound has been made as a disodium salt but the most
recent theory is that it exists because it is stabilized by interactions
with counterions: J. Chem. Theory Comput. 2013, 9, 4436−4443.
“Like many multiply charged anions, COT2− exists in
isolation only as a short-lived resonance state lying
above neutral COT.”
“….Charge-compensating complexation of COT2−with
two sodium cations results in a thermodynamically
stable Na2COT compound”
Reply
James Ashenhurst
September 18, 2019 at 10:08 am
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Very interesting! Also from the paper: “Comparison with all-


trans octatetraene indicates that COT2− has a substantial
Master aromatic stabilization energy (25 kcal mol−1) approaching
Organic that of benzene (33 kcal mol−1), but this favorable influence is
Chemistry
swamped by Coulomb repulsion. “
 Previous Reply 

Mike Turner
February 5, 2020 at 12:20 pm
TYPO: Note 2 line 1 “The stability arising from antiaromaticity in the
cyclobutadiene dication ” should refer to aromaticity.
Overall this is an excellent series of articles.
Reply
James Ashenhurst
February 12, 2020 at 11:55 am
Fixed it, thank you!
Reply

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