324 ChemActivity 17: Conjugation and MO Theory

The Big Picture

Molecular orbital theory is a tool that is used more frequently in advanced organic courses than in this
course. This activity is designed as a brief introduction to the topic. Though you may be asked to
generate a simple MO diagram of the pi system of a small symmetrical molecule, generating an MO
diagram of a complex or asymmetrical molecule is a task beyond the scope of this course. Most
predictions we will make in this course will use the older, simpler tools we have become familiar with
like Lewis structures, resonance structures, and hybridization.
The key exception appears in the next activity, in which we use MO theory to explain why benzene and
other so called “aromatic” molecules are unusually stable and low in energy.
UV-visible spectroscopy is mostly used to determine energy gaps on an MO diagram (e.g., the
difference between the HOMO and the LUMO. This can tell you about the symmetry of a molecule, but
does not give direct structural information like IR, NMR, and MS.

Common Points of Confusion

p orbitals can be conjugated only when they are parallel and neighbor one another.
MO theory relies on the wave nature of electrons, which is very strange and abstract. Accept on faith
the strange premises of MO theory, for example…
• An electron can be delocalized over all lobes of a molecular orbital. (You may want to think
of it as a fine mist of negative charge rather than a discrete particle.)
• An electron can be found in either lobe of a p orbital, but can NEVER be found on the node
separating these lobes. (In fact, the electron is said to move from one lobe to the other via
something called quantum mechanical “tunneling.”)
• A molecular orbital can exist without any electrons in it. Think of it as a sort of ghost orbital
that has no effect until it is populated with one or two electrons.
• Multiple molecular orbitals can exist in the same region of space, even when both are
populated with electrons. For example, the two π bonding orbitals in Figure 17.4 occupy
approximately the same space.
• In the next activity we will see symmetrical MO diagrams in which two different MO’s have
exactly the same potential energy. These are called “degenerate MO’s”—this name comes
from the mathematics and is not a moral condemnation of these molecular orbitals.
ChemActivity 18: Aromaticity

PART A: AROMATICITY
(What structures are likely to exhibit the special stability known as aromaticity?)

Model 1: Amazing Benzene!

=
benzene

H2
H2 -54 Rho
Pto kcal/mole ?
H2 -28 o
or H2/Pt
hydrogenation Pto kcal/mole at high pressure
product
(cyclohexane)

Figure 18.1: Heats of Hydrogenation

Critical Thinking Questions

It turns out that it is much faster to
1. (E) What property of draw a solid-line circle so you will
benzene does the dotted- often see benzene drawn this way
line circle emphasize?

2. Based on the data in Figure 18.1, estimate the heat of hydrogenation for benzene. (Note that it
takes an exotic rhodium catalyst or extreme conditions to reduce benzene to cyclohexane.)

3. The heat of hydrogenation of benzene is actually 49kcal/mole.

a. Add a solid line to Figure 1 indicating this value for benzene.
b. Is benzene more or less stable than predicted based on the heats of hydrogenation of
cyclohexene and 1,3-cyclohexadiene?

Term Introducton: Aromatic Molecules and Aromaticity

• Benzene and other similar molecules exhibit an almost magical stability (lower than expected
potential energy). These molecules are called aromatic molecules.
• Before it was understood, this “magical stability” was named aromaticity because many
molecules in this class have a strong aroma (smell).
• Resonance alone cannot explain this amazing stability.
326 ChemActivity 18: Aromaticity

Model 2: Cyclic Conjugated π Systems (“Racetrack” Analogy)

Recall from ChemActivity 5 that an electron in a larger “box” has a longer wavelength and so is lower
in potential energy than an electron confined to a smaller “box.”
The “racetrack” analogy states that the electrons of benzene are low in P.E. because they reside in a
“box” that is effectively very large due to the fact they can race endlessly around a track of conjugated
p orbitals. We call this “racetrack” of p orbitals a cyclic conjugated pi system.

Racetrack
is the electrons go
same as... round and round
Aromatic Conjugated π System

not a
can be represented as... racetrack!
Normal Conjugated π System

Not all cyclic conjugated π systems are aromatic. Only those structures below that are labeled
“Aromatic” display the special stability associated with aromaticity.

aromatic aromatic aromatic aromatic

Figure 18.2: Examples of cyclic conjugated π systems

Critical Thinking Questions

4. Confirm that there is a p orbital (empty or half-filled) at each carbon in Figure 18.2.
a. Find the largest possible cyclic conjugated π system in each molecule in Figure 18.2, and
label it with the total number of electrons in that π system (the electrons in the p orbitals
of the largest racetrack).
b. Certain “magic numbers” of π electrons give rise to aromaticity. According to the data in
Figure 18.2, circle the “magic numbers” in the list below.
2 4 6 8 10 12 14 16 18 20

c. Continue the series past 10 electrons: Which of 12, 14, 16, 18, and 20 appear to fit the
pattern and are expected to be "magic" numbers that allow aromaticity. Circle these above.

d. Which of the following molecules is expected to be

aromatic? Explain your reasoning.
 ChemActivity 18: Aromaticity 327

Memorization Task 18.1: Hückel’s Rule

In 1938 German chemist Erich Hückel noticed that molecules with 2, 6, 10, 14, 18, 22, etc., electrons in
their cyclic conjugated π system displayed the special properties of aromatic molecules.
This came to be called “Hückel’s Rule,” which states: “a cyclic, continuous, conjugated π system
exhibits aromaticity (special stability) if it contains 4n + 2 π electrons (where n = 0, 1, 2, 3…etc.).”

Critical Thinking Questions

5. (Check your work.) Are your answers on the previous page consistent with Memorization Task
18.1?

6. For a molecule to be considered aromatic it must simply contain an aromatic π system.

(That is, there can be parts of an aromatic molecule that are not involved in the “racetrack.”)
a. Cross out the three molecules below that are not aromatic (non-aromatic).
b. Trace each aromatic π system ("racetrack") in the remaining (aromatic) molecules. The first
two are done for you. Note that the second example has two aromatic rings. Even though
these two aromatic rings are conjugated together, they are NOT considered a single aromatic
system (The molecule has two separate aromatic "racetracks.").

7. A molecule is aromatic if it has at least one resonance structure with a continuous cyclic π system
containing 4n+2 π electrons. The cation below is aromatic, but the resonance structure shown does
not demonstrate this! (It does NOT contain an aromatic π system). Draw a different resonance
structure of this molecule that contains an aromatic π system and shows this cation is aromatic.

Note: There are a total of 11 resonance structures

in this set. Only four of them contain an aromatic
pi system. Draw them at home for practice.

a. How many π electrons are involved in the aromatic resonance structure you drew?

b. Which of the two resonance structures shown is more important? Explain your reasoning.
328 ChemActivity 18: Aromaticity

8. Consider the orbital representations of benzene below.

= or

benzene
planar not planar
a. Which π system (planar or not planar) has the better p orbital racetrack?

b. Is your conclusion consistent with the fact that benzene is always planar?

c. Construct an explanation for why all conjugated π systems (not just aromatic ones) are lower
in potential energy when they are planar.
O

For Example: For both: All atoms lie in

the plane of the paper.

Memorization Task 18.2: Rule for determining when a lone pair will reside in a p orbital
A lone pair on an atom in a cyclic conjugated π system will occupy a p orbital (and become a part of
the π system of the molecule) if doing so makes the molecule aromatic.

9. Construct an explanation for why an sp3 hybridized atom in a ring interrupts any “p orbital
racetrack” in that ring. (See last two examples in CTQ 6.)

10. Calculate the number of electrons in the π system of each

molecule at right if… NH
NH
a. the lone pair on N resides in a p orbital.

b. the lone pair on N resides in an sp3 hybrid orbital (does not participate in the π system).
c. Predict which lone pair at right will reside in a p orbital and which will reside in an sp3
hybrid orbital, and explain your reasoning.
 ChemActivity 18: Aromaticity 329

11. Construct an explanation for why the lone pair on N in the molecule below CANNOT participate
in the π system of the molecule (even though doing so would give the molecule 4n+2 π electrons).
Hint: There is already a p orbital on the nitrogen. What is this p orbital doing?)

12. In the following molecule only one of the lone pairs on oxygen resides in a p orbital.
a. Explain why one lone pair on oxygen resides in a p orbital.
O

b. What is the hybridization state of the oxygen, and what type of orbital does
the other lone pair on oxygen occupy?

13. Can the following molecule be aromatic? Explain your reasoning.

14. Indicate the type of orbital holding each lone pair, and label each molecule that is aromatic.
H

N O N

N N

15. Review: For a molecule to be aromatic it must have a π system that …(fill in the blanks).
(1) is cyclic
(2) has a continuous set of ____________________ p orbitals (no sp3 carbons in the ring)
(3) has __________ π electrons (2 or 6 or 10 or 14, etc.)
(4) and has an overall ________________ geometry allowing the p orbitals to be parallel.
330 ChemActivity 18: Aromaticity

PART B: MO EXPLANATION FOR AROMATICITY

(How can we explain aromaticity and anti-aromaticity using molecular orbital theory?)

Model 3: Molecular Orbital Diagrams of Cyclic π Systems

The MO diagram of a cyclic conjugated π system takes the shape of the ring involved, with one vertex
pointing down. For example…

MO Diagram of Benzene MO Diagrams of Other Cyclic Conjugated Pi Systems

(completed) (electrons not f illed in yet)
Figure 18.3: MO diagrams of cyclic conjugated π systems

Molecular orbitals on a MO diagram with the same energy are called degenerate orbitals.
All degenerate orbitals must be half-filled before any one is filled. For example…
Valence Electron Orbital Occupation for a Oxygen Atom

2px 2py 2pz 2px 2py 2pz

(Three degenerate p orbitals) (Three degenerate p orbitals)
2s 2s

CORRECT not correct

Critical Thinking Questions

16. Circle a pair of degenerate molecular orbitals on the MO diagram of benzene.
17. Add the appropriate number of electrons to the three other MO diagrams in Figure 13.3.

Memorization Task 18.3: Radical Character

A species with an unpaired electron is said to have "radical character." Usually a species with radical
character is very reactive.

18. Label two compounds in Figure 13.3 with the words “has radical character-very reactive.”

19. Employing Hückel's Rule, label all aromatic species in Figure 13.3.
 ChemActivity 18: Aromaticity 331

# Atoms
in Ring 7 8 9 10
Figure 13.4: MO diagrams of 7-, 8-, 9-, and 10-atom cyclic conjugated π systems

20. Use the MO diagram of an 8-atom ring (above) to fill in the following table.
No. Of Electrons in the π System 2 4 6 8 10 12
Has Radical Character According to MO
Aromatic (according to Hückel's Rule)

21. Confirm that you get the same answer to the previous question no matter which cyclic MO
diagram you use to fill in the table (as long as there is room for all the electrons).

Term Introduction: Anti-Aromatic Molecules

A molecule is anti-aromatic (and highly reactive) if it exhibits all characteristics of aromaticity
EXCEPT that it has 4n (instead of 4n+2) π electrons (e.g., 4, 8, 12, etc.).

22. Label each species in Figure 18.3 that is anti-aromatic.

23. Cyclobutadiene can be isolated and studied at temperatures lower than 200oC. At temperatures
above 200oC it immediately reacts with itself to form other more stable products. Use molecular
orbital theory to explain why cyclobutadiene is unstable.

Cyclobutadiene (very unstable)

24. List four things about cyclobutadiene that make it anti-aromatic.

332 ChemActivity 18: Aromaticity

25. (Check your work.) Compare your answer to the previous CTQ to the last CTQ in Part A.

26. Cyclooctatetraene is quite stable at room temperature. However, close examination of the
structure reveals that it is not planar. This can be explained by optimization of bond angles.

Cyclooctatetraene in its
Cyclooctatetraene Preferred Conformation
a. Use MO theory to construct an argument not based on bond angle optimization that
explains why cyclooctatetraene is not planar.

b. Cyclooctatetraene is considered non-aromatic. This means it is neither aromatic nor anti-

aromatic. Explain.

27. Cyclobutadiene is one of the few molecules that is unable to “avoid” being anti-aromatic. Explain.

28. Construct an explanation for

why the N on the following NH
molecule is expected to be sp3
hybridized.

Memorization Task 18.5: Most molecules are non-aromatic & very few are anti-aromatic.
Cyclobutadiene is too small to adopt a nonplanar geometry. Most other cyclic conjugated π systems
with 4n π electrons can flex to adopt a conformation that is not planar, or adopt a hybridization state
that breaks the conjugated π system.
Bottom line: There are very few anti-aromatic molecules and many aromatic molecules, but the
majority of molecules are neither aromatic nor anti-aromatic (these are called non-aromatic).

29. Draw an example of each of the following that does not already appear in this activity: an anti-
aromatic molecule, an aromatic molecule, and a non-aromatic molecule.
 ChemActivity 18: Aromaticity 333

Exercises for Part A

1. Only one of the following molecules is aromatic. Label it aromatic.

2. Indicate the largest aromatic ring in each of the following aromatic molecules.

Br

Cl

3. Draw the enol form of the following ketone, and construct an explanation for why the enol form is
favored in this special case. (Recall that normally the keto form is lower in potential energy and
therefore favored.)
O

tautomerize
keto form enol form
(favored in this case!)

4. For a set of resonance structures, the members of the set that are aromatic are considered lower-
potential-energy arrangements of the electrons. These aromatic resonance structures are therefore
considered "more important" than their non-aromatic counterparts. For each of the following,
draw all important resonance structures, and mark the ones that are more important (aromatic).
Br

5. Explain why each of the following structures (as shown) is NOT aromatic.