Ace Your Next Organic Chemistry Exam.: Aromaticity
Ace Your Next Organic Chemistry Exam.: Aromaticity
Ace Your Next Organic Chemistry Exam.: Aromaticity
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The trick is called “Frost Circles”, or, sometimes, the “Polygon method”.
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The Molecular Orbitals Of Benzene Can Be Superimposed On A Hexagon With the
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Useful observation: these energy levels can be superimposed on a hexagon with the
vertex pointing down. Like this!
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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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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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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
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the pi electrons and sigma electrons separately. It’s a powerful and useful method
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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
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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