Aromaticity

Aromatic compounds
Natural oils from Plants
Natural oils from Plants
Balsams, Resins or Essential oils
Discovery of Benzene
Discovery of Benzene
Unusual Reactivity of Benzene
The Kekule Structure of Benzene (1865)
Structure with alternate single and double bonds
Structure with alternate single and double bonds
Enthalpy of Hydrogenation‐ Stability of Benzene
Resonance (or Stabilization) Energy of Benzene
Resonance Theory for Structure of Benzene

(not )
I II

H H
C C 120°
H C C H
1 09 A
1.09
C C
1.39 A III
H H
Resonance Hybrid
C-C single bond = 1.47 A
C=C double bond = 1.34 A

1,3,5-cyclohexatriene
Molecular Orbital Theory for Structure of Benzene
Molecular Orbital Theory for Structure of Benzene
Electronic Configuration by Molecular Orbital Theory for Benzene

gy
Energ
 Huckel’s Rule: The (4n+ 2) π Electron Rule

1931, German
1931 G physicist
h i i t Erich
E i h Huckel
H k l
Planar monocyclic rings, with each atom having a p orbital
(4n+2) π electrons; n=0,1,2,3 etc.,
Planar monocyclic rings with 2, 6, 10, 14, 18… delocalized electrons
should be aromatic
 π Molecular orbitals of Benzene by 
o ecu a o b ta s o e e e by
polygon and circle method

Antibonding orbitals

(Nonbonding orbital)

Bonding
g orbitals

Polygon in circle Energy levels Type of orbital

of MOs

Aromatic, 6 π electrons
π Molecular orbitals of Cyclooctatetraene
Molecular orbitals of Cyclooctatetraene (planar)

Non‐aromatic, 8 π electrons
Non‐planar
Non planar Cyclooctatetraene
Cyclooctatetraene
Annulenes
 [10]Annulenes
[10]annulenes; predicted to be aromatic
However, non-planar and non-aromatic

H H
H

H
H

H
all cis double bonds
two trans double bonds bond angle ~144°,
~144° high angle strain,
strain
bond angle ~120°, no angle strain, non-planar, no p orbital overlap
steric crowding of two H's, non-planar
no p orbital overlap
H

one trans double bond

bond angle ~144°, high angle strain,
non-planar, no p orbital overlap
Aromatic Ions
Aromatic cation

+
Aromatic, Nonaromatic and Antiaromatic compounds
Aromatic, Nonaromatic
, and Antiaromatic compounds
p
Polycyclic benzenoid aromatic hydrocarbons (PAHs)
Polycyclic benzenoid aromatic hydrocarbons (PAHs)
 p orbitals of Naphthalene
H H
H C 8a C H
C C C
C C C or
H C 4a C H
H H
Naphthalene
10 electrons
(aromatic)
Application of Huckel’s Rule
Application of Huckel’s
Nonbenzenoid aromatic compounds
aromatic compounds
 Buckminster Fullerenes

C60, 20‐hexagons, 12‐pentagons, 
C70, 25‐hexagons, 12‐pentagons, 
sp2 hybridisation, doesn’t exhibit
sp2 hybridisation
superaromaticity, e’s in the 6‐member ring
doesn’t delocalize over whole molecule
 Chemistry of Fullerenes
 Fullerenes have a high electron affinity
 Readily accepts electron from alkali metal‐metallic phase‐”buckide
salt”
 K3C60 is a stable metallic crystal consisting of ‘fcc’ structure of ‘bucky
balls” with K+ ions in between
 K3C60 becomes superconductor below 18 degree Kelvin
Heterocyclic Aromatic Compounds
Heterocyclic Aromatic Compounds
p orbital structure of pyridine
bit l t t f idi
p orbital structure of pyrrole
orbital structure of pyrrole

p orbital

N H
N H

Pyrrole
p orbital structure of furan and thiophene

p orbital

O S

sp2 orbital
(orthogonal to
p orbitals)
bit l )
Thiophene
Aromatic compounds in Biochemistry