Why do we see that part of the spectrum?

trans-retinal cis-retinal
O
© Philip Jessop, 2018
Benzene

August Kekulé
1829-1896
 Resonance Stabilization in Benzene

+ 3H2 + heat

resonance stabilization
energy
151 kJ
-359 kJ
-239 kJ
-208 kJ
-232 kJ
-119.7 kJ

http://www2.latech.edu/~hji/org252/10apr18/10apr18.html
 Benzene
[6 x 4(C)] + [6 x 1(H)] = 30 valence electrons

6 C-C σ bonds = 12 e
6 C-H σ bonds = 12 e
3 C-C π bonds = 6 e
 Benzene – p MOs

π6

π4 π5

π2 π3

π1

6 π electrons gives stability http://www.catalysis.nl/~chembond/notes/benzene/benzene.html

Benzene – p MOs

π6

π4 π5

π2 π3

π1

http://www.catalysis.nl/~chembond/notes/benzene/benzene.html
Benzene vs. Cyclooctatetraene
 Cyclobutadiene
H H

H H

π4

π2 π3

π1

4 π electrons gives instability

 Cyclopentadienyl anion
H H
C strong base C
HC HC
CH2 CH
HC HC H H
C C C C
H H HC HC
CH CH etc.
HC HC
C C
H H

π4 π5

π2 π3

π1
6 π electrons gives stability
 H2
C
HC CH

HC CH

-H- -H• -H+

H H H
C C C
HC CH HC CH HC CH

HC CH HC CH HC CH

Cyclopentadienyl cation Cyclopentadienyl radical Cyclopentadienyl anion

π4 π5 π4 π5 π4 π5

π2 π3 π2 π3 π2 π3

π1 π1 π1

4 or 5 π electrons gives instability 6 π electrons gives stability

 Cycloheptatriene
H H

-H- -H• -H+

H H H

tropylium cation
 Aromatic molecules and Frost Circles

How many electrons are

needed to avoid SOMO
and π* orbitals?
n=3 n=4
2, 6, or 10
C3H3+ C4H42+

n=5 n=6 n=7 n=8

C5H5- C6H6 C7H7+ C8H82+

 Hückel s Rule for Aromaticity
1. 4n + 2 p-electrons where n is a non-negative integer
2. Cyclic arrangement of p orbitals
3. Ring MUST be planar
4. Every atom must have a p orbital ^ to the plane of
the molecule (sort of)

CH2 CH
 Other aromatic systems
H
Cyclopropenyl cation, C3H3+, 2 p electrons

H H
 Polyaromatic Hydrocarbons (PAH)
Catacondensed

Phenanthrene

Naphthalene Anthracene

Chrysene
Tetraphene
Pericondensed

Pyrene Perylene Coronene Antanthrene

 Polyaromatic Hydrocarbons (PAH)
Planar

Coronene Antanthrene

Bowl-shaped

Corannulene
Graphene
Graphite
Graphene isolation
Carbon nanotubes
 Fullerenes

Buckminster Fuller Harry Kroto

1895-1983 1939-

C60
 Antiaromatic molecules
1. 4n p-electrons where n is a non-negative integer
2. Cyclic arrangement of p orbitals
3. Ring MUST be planar
4. Every atom must have a p orbital ^ to the plane of
the molecule (sort of)

Which of these molecules are antiaromatic?

Cyclopentadienyl
 Heteroatoms with normal conjugation
Lone pair (if there is one) goes in an sp2 orbital, does NOT add e to
the π system
lone pair
in sp2 orbital

N Si H

pyridine silabenzene

N Si H
 Heteroatoms with cross-conjugation

One lone pair goes in an unhybridized p orbital, adds 2e to the π system

lone pair
lone pair in p orbital
in p orbital

N H O

2nd lone pair

in sp2 orbital
pyrrole furan

N H O
 Cross-conjugation with exocyclic double bond

π electrons in the exocyclic double bond do NOT add to the π ring system.

π ring system contains

Exocyclic π e do NOT
how many π e?
Add to π ring system

C O
O
O
O 2nd lone pair
lone pair in sp2 orbital
2-pyrone
in p orbital
 3rd Period and Below
• Hybridization in 3rd period takes more energy than in 2nd period.
• Aromaticity does not require hybridization, but it does require an unhybridized p.
aromatic not aromatic

HYBRIDIZED AND HYBRIDIZED BUT

AROMATIC NOT AROMATIC
hybridized

Me Me
Cl
Et3N P
Me N N
P Cl + NH4Cl
Me - 4 Et3NHCl Me Me
Cl S P P
N
Me Me

UNHYBRIDIZED AND UNHYBRIDIZED

unhybridized

AROMATIC NOT AROMATIC

Bi P
H
 3rd Period and Below

HYBRIDIZED AND
AROMATIC
S
2-
X

Ga

Ga Ga
S Se X X

thiophene selenophene cyclogallane

+ Si H
B
Si B B
P
H
phosphinine silabenzene B3+ cation
 3rd Period and Below B
B B
HYBRIDIZED AND
AROMATIC sp2 hybridization

2-
X B
Ga B B
Ga Ga
S Se X X for σ bonds
thiophene selenophene cyclogallane
B
+
B B B
Si B B
P for π bonds
H
phosphinine silabenzene B3+ cation Two sp2 orbitals have an electron.
Third sp2 orbital is empty.
The unhybridized pz has an e.
 3rd Period and Below

UNHYBRIDIZED AND
AROMATIC

2-
Al Al

Al Al
Bi
Bi

bismabenzene

2-
As
As As As
As 1e in each p orbital (green, blue and red).
As As As 2e in lone pair s orbital (not shown)
As
 3rd Period and Below

UNHYBRIDIZED AND [Al42-]

AROMATIC

2-
Al Al

Bi Al Al
for σ bonds for σ bonds
bismabenzene

2-
As
As As As
As
As As As
As

for π bonds
 3rd Period and Below
Me Me
Cl
Et3N P
HYBRIDIZED
Me
P Cl + BUT
NH4Cl N N
NOTClAROMATIC
Me - 4 Et3NHCl Me
P P
Me
N
Me Me

Me Me
P
N N
Me Me
P P
N
Me Me
 3rd Period and Below

UNHYBRIDIZED
NOT AROMATIC
H
P
H
As
H
P
phosphole arsole

1e in each p orbital (green, blue and red).

2e in lone pair s orbital (not shown)