Molecular Orbitals: 1,3,5-hexatriene

π6 π6

Antibonding
π5 π5
(LUMO)

π4 π4
(LUMO) (HOMO)
Energy

π3 π3

(HOMO)

Bonding
π2 π2

π1 π1
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Ground
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Molecular Orbitals: 1,3,5-hexatriene

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π-MO of benzene and 1,3,5-hexatriene

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π-MO of benzene and 1,3,5-hexatriene

The cyclic π-system is stabilized relative to the acyclic one

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π-MO of benzene

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Molecular Orbitals - Benzene

π6 Antibonding

π4 π5

Non-bonding
E
π2 π3

π1 Bonding

Benzene’s 6π electrons fill the 3 bonding orbitals; antibonding orbitals are vacant
“CLOSED BONDING SHELL” – STABLE!
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Practice

Draw the molecular orbital diagram and energy

level diagram for cyclobutadiene.

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π-MO of cyclobutadiene

ABMO

π4

π2 π3 NBMO

π1

E BMO

This diradical would be very reactive

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An Easier Way to Draw the MOs?
Frost’s Circle Method

π6 π4

Antibonding
π4 π5

Nonbonding π2 π3

π2 π3
Bonding

π1 π1

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 Practice
Draw the MOs including their energy (using the Frost Circle Method ) for
Cycloheptatrienylium ion (tropylium ion)

π6 π7 π6 π7

π4 π5 π4 π5

π2 π3 π2 π3

π1 π1

Is it aromatic or antiaromatic
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 Practice
Draw the MOs including their energy (using the Frost Circle Method ) for
Cycloheptatrienyl anion

π6 π7 π6 π7

π4 π5 π4 π5

π2 π3 π2 π3

π1 π1

Is it aromatic or antiaromatic
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Definition of Aromatic Compounds
o The structure must be cyclic, conjugated π-bonds
o Each atom in the ring must have an unhybridized p-orbital
o The structure must be planar (or nearly planar) for effective
overlap
o Delocalization of the π-electrons over the ring must lower the
resonance energy

Hückel’s Rule (Resonance + MO considerations)

Once the above criteria are met, Huckel’s rule applies:

(4n+2)-π electron system : Aromatic

(4n)-π electron system : Antiaromatic
where ‘n’ is integer
If, above criteria are not met then the system is non-aromatic
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Examples: 2π electron system
Non aromatic
Reason: No uninterrupted ring of p-orbital bearing atoms

Cyclopropenyl cation

Resonance
Resonance Contributors Hybrid
Aromatic

Cyclopropenyl anion Antiaromatic

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4π electron system
Annulenes – Monocyclic structures with complete conjugation i.e.
Alternate single and double bonds

Represented as [n]-Annulene

No. of C atoms in the ring

Cyclobutadiene ([4]-Annulene)
Nonaromatic
1.57 Å
1.34 Å Aromatic

Antiaromatic Aromatic Antiaromatic

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6π and 8π electron system
6π electron system H H H
H
H
H H
H
Nonaromatic Aromatic Homoaromatic

8π electron system
• Cyclooctatetraene ([8]-annulene)

H 1.33 Å
117.6°
135°

1.46 Å 126°
Nonaromatic
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10π electron system
Cyclodecapentaene ([10]-Annulene)

154° Aromatic ?

H
H Non aromatic

Electrocyclic
Δ
ring closure

H
Aromatic

H
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Aromatic Heterocyclic Ring Systems
N
• Resonance energy of pyridine is
N N 134 kJ (32 kcal)/mol
Pyridine Pyrimidine

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Aromatic Heterocyclic Ring Systems
N No contribution
Pyrrole Imidazole
N N
H H contributes

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Aromatic Heterocyclic Ring Systems

O S
Furan Thiophene

§ Resonance energy of furan is 67 kJ (16 kcal)/mol

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Aromatic Heterocyclic Ring Systems

N
§ LP doesnot contribute to π-system
N
Pyridine Pyrimidine

N § LP contribute to π-system
H
Pyrrole

No contribution
N S O
Thiophene Furan
N
H contributes
One LP contributes
Imidazole

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Interesting Fused Systems

Azulene

Triapentafulvalene

Stabilizing dipolar resonance structures

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