Chem 242 Spring 2008

Answers to Problem Set 4

Question 1. Provide molecular orbital diagrams for each of the following compounds. In
addition, label each compound as aromatic, antiaromatic or nonaromatic (nonaromatic
compounds are neither aromatic or antiaromatic).

A B C D E

aromatic antiaromatic antiaromatic aromatic nonaromatic

2 3

2 3

1
Chem 242 Spring 2008

4 5

2 3

4 5

2 3

1
Chem 242 Spring 2008

1
Chem 242 Spring 2008

Question 2. Classify the following molecules as aromatic, antiaromatic or nonaromatic.

Give an explanation for your answer. The last one is very tricky

H sp3 carbon

10e-, aromatic nonaromatic 12e-, antiaromatic

N
N
O
H
6e-, aromatic (the oxygen
12e-, antiaromatic 10e-, aromatic (the nitrogen
contribues 2 e-)
contributes 2 e-)

H
H

nonaromatic (see below)

For this molecule to be planar, the two hydrogens indicated above would have to occupy the same
space. Therefore, even though the -system would contain 10e-, geometric restraints force the
molecule to twist and disrupt the continuous -overlap. A tricky problem!!!
Chem 242 Spring 2008

Question 3. Which of the following compounds is more basic (i.e., which lone pair of
electrons shown below is more likely to become protonated)? Clearly explain your
choice.

Me Me
O

4-pyrone acetone

H H
O O

more basic + other resonance structures

O O

6e-, aromatic
multiple resonance structures stabilize the protonated form; the aromatic resonance structure is
particularly stable

H H
O O
less basic

Me Me Me Me

only one resonance structure stabilizes the protonated form

Chem 242 Spring 2008

Question 4. Why does the following compound have a large molecular dipole?

azulene

6e-, aromatic 6e-,

aromatic
Chem 242 Spring 2008

Question 5. Rank the following compounds from most to least basic. Clearly explain
your reasoning.

N N
N
H H

pyridine pyrole pyrolidine

most basic pyrolidine has a very basic sp3-hydrbridized lone pair. Aromaticity is not
N a consideration.

pyridine is less basic than pyrolidine becuase the lone pair is in an sp2-
hydrbidized orbital**. However, protonation of the nitrogen does not
disurpt the aromatic -system.
N

least basic pyrole is not very basic becuase the lone pair on nitrogen is involved in -
bonding with the aromatic system. Protonation disrupts the aromaticity.
N

** Why does hybridization matter? That's an excellent question. Can you think of any other topics
that we have discussed where this is true?