BENZENE AND AROMATICITY

CHE 212

1
 Benzene’s Unusual Structure
❑ All its C-C bonds are of the same length: 139 pm — between
single (154 pm) and double (134 pm) bonds

❑ Electron density in all six C-C bonds is identical

❑ Structure is planar, hexagonal

❑ C–C–C bond angles 120°

❑ Each C is sp2 and has a p orbital perpendicular to the plane of the

six-membered ring

2
Bond distances and Bond Angles of
Benzene

3
 Drawing Benzene and Its Derivatives
❑ The two benzene resonance forms (canonical forms) can be
represented by a single structure with a circle in the center to
indicate the equivalence of the carbon–carbon bonds

❑ This does not indicate the number of  electrons in the ring but
reminds us of the delocalized structure

❑ We shall use one of the resonance structures to represent benzene

for ease in keeping track of bonding changes in reactions

4
 Unusual Reactions
❑Alkene + cold/dil KMnO4 → diol (addition)
Benzene + KMnO4 → no reaction.
❑Alkene + Br2/CCl4 → dibromide (addition)
Benzene + Br2/CCl4 → no reaction.
❑With FeCl3 catalyst, Br2 reacts with benzene
to form bromobenzene + HBr
(substitution reaction!). Double bonds
remain.
=>
5
 Unusual Stability
❑Hydrogenation of just one double
bond in benzene is endothermic!

=>
6
 MO Rules for Benzene
❑Six overlapping p orbitals must form six
molecular orbitals.

❑Three will be bonding, three antibonding.

❑Lowest energy MO will have all bonding

interactions, no nodes.

❑As energy of MO increases, the number of nodes

increases.
7
 Molecular Orbital (MO) Energy Diagram for
Benzene
❑The six electrons fill three bonding pi orbitals.

❑All bonding orbitals are filled (“closed shell”),

an extremely stable arrangement.
❑HOMO stands for highest occupied molecular
orbital
❑LUMO stands for lowest unoccupied molecular
orbital
Consider benzene. Since each of the six carbon atoms in benzene
has a p orbital, six atomic p orbitals combine to form six  MOs.

To fill the MOs, the

six electrons are
added, two to an
orbital. The six
electrons
completely fill the
bonding MOs,
leaving the anti-
bonding MOs
empty. All bonding
MOs (and HOMOs)
are completely
filled in aromatic
compounds. No 
electrons occupy
antibonding MOs.

9
Energy Diagram for Benzene

=>

10
 Energy Diagram for Cyclobutadiene
❑Following Hund’s
rule, two electrons
are in separate
orbitals.
❑This diradical
would be very
reactive.
MO’s for Cyclobutadiene

12
Frost Circles: relative energies of the molecular orbitals of
cyclic, fully conjugated systems

Inscribe the cyclic, conjugated molecule into a circle so

that a vertex is at the bottom. The relative energies of the
MO’s are where the ring atoms intersect the circle benzene:

The bonding MO's will be filled for aromatic compounds,

such as benzene.
 Polygon Rule
❑The energy diagram for a cyclic fully conjugated
system has the same shape as the cyclic
compound with one vertex at the bottom.
 Aromatic Requirements
❑Structure must be cyclic with conjugated
pi bonds. Each atom in the ring must have an
unhybridized p orbital which must overlap
continuously around the ring.

❑Must be planar or flat

15
 Hückel’s Rule
❑If the compound has a continuous ring of
overlapping p orbitals and has 4n + 2 pi electrons
then it is aromatic.
❑If the compound has a continuous ring of
overlapping p orbitals and has 4n pi electrons then
it is antiaromatic.

16
MO Derivation of Hückel’s Rule
• Lowest energy MO has 2 electrons.
• Each filled shell has 4 electrons.

Chapter 16 =>17
 Anti- and Nonaromatic
❑Antiaromatic compounds are cyclic, conjugated,
with overlapping p orbitals around the ring, but the
energy of the compound is greater than its open-
chain counterpart.

❑Nonaromatic compounds do not have a continuous

ring of overlapping p orbitals and may be
nonplanar.

18
 Annulenes
❑Annulenes - monocyclic, conjugated, planar
polyenes that conform to Hückel's rule. Written
as [N]annulene. N is the number of pi electrons

❑[4]Annulene is antiaromatic (4 pi e-’s)

❑[8]Annulene would be antiaromatic, but it’s not

planar, so it’s nonaromatic.

❑[10]Annulene is aromatic except for the isomers

that are not planar.
Annulenes - monocyclic, conjugated, planar polyenes that
conform to Hückel's rule.
[10]annulene [14]annulene [18]annulene

10 -electrons
4n+2 = 10, n=2. 14 -electrons 18 -electrons
4n+2=14, n=3
4n+2=18, n=4

[16]annulene
16 -electrons
20
4n=16, n=4
 Aromaticity for Ions:
Cyclopropenyl anion

4n=4
n=1
anti-aromatic

Cyclopropenyl cation

4n+2=2
n=0
aromatic

21
 Cyclopentadienyl anion

4n+2=6
n=1
aromatic

Cyclopentadienyl cation
4n=4
n=1
anti-aromatic

22
 Cyclopentadienyl Ions
❑ The cation has an empty p orbital, 4 electrons, so
antiaromatic.
❑ The anion has a nonbonding pair of electrons in a p orbital, 6
e-’s, aromatic.

=>

23
Resonance Depictions of the Ions
Cycloheptatrienyl anion

4n=8
n=2
Anti-aromatic

Cycloheptatrienyl cation

4n+2=6
n=1
aromatic

25
 Tropylium Ion
❑The cycloheptatrienyl cation has 6 p electrons
and an empty p orbital.
❑Aromatic: more stable than open chain ion

H
H OH
+
H , H2O +

26
 Dianion of [8]Annulene
❑Cyclooctatetraene easily forms a -2 ion.
❑Ten electrons, continuous overlapping p
orbitals, so it is aromatic.

❑
+
+ 2K + 2K

27
 Which of these compounds is aromatic?

CH2

A B

A) Is aromatic. Count the number of pi bonds in

the outer ring. A has 5 which means 10 pi
electrons, 4(2)+2=10. While B has 6 pi bonds and
12 pi electrons, 4(3)=12. Doesn’t meet the
Huckel rule requirements for aromaticity.
28
 Is this compound aromatic or antiaromatic?

Antiaromatic – cyclic, planar, conjugated , but

does not meet Huckel’s rule.
4 doulbe bonds and 2 triple bonds so 4(2) +
2(4)=16 pi electons. 4n+2 or 4n? 4(4)=16

29
Indicate which of the following are aromatic and
antiaromatic?

B
A

C is aromatic 4(3)+2=14
A is antiaromatic 4(2)=8 30
Which of the following is aromatic?

A B

C D

C is aromatic 10 pi electrons, 4(2)+2=10 and

completely conjugated b/c lone pair is in a p
orbital.
Which are antiaromatic?
Which of these is antiaromatic?

A B

D
C

B 8 pi electrons 4(2)=8

C and D as well, 8 and 4 respectively

32
 Pyridine
• Heterocyclic aromatic compound.
• Nonbonding pair of electrons in sp2 orbital,
so weak base, pKb = 8.8.

33
 Pyrrole
Also aromatic, but lone pair of electrons is
delocalized, so much weaker base.

=>
34
 Basic or Nonbasic?
Pyrimidine has two basic
N N
nitrogens.

N N H
Imidazole has one basic
nitrogen and one nonbasic.

N
N
Purine?
N N =>
H 35
 DNA & RNA Bases Are
Purine bases Aromatic Pyrimidine bases

These heterocycles are aromatic because of amide

resonance:

36
Other Heterocyclics

=>
37
 Aromatic?

BH
a) b) c) O
NH
 Aromatic, Anti-Aromatic or
Nonaromatic?

H
N
a) b) c)

N
H