Dr. K.

Tharanikkarasu (Units – III)

Structural feature of aromatics
3/24/2023 1
 Syllabus
Unit III Structural feature of aromatics –
Aromaticity characteristic features,
annulene, benzenoid, nonbenzenoid,
heteroaromatics, charged aromatics,
fulvenes, fulvalenes, anti aromatics and
homoaromatics.

3/24/2023 2
 Aromaticity of Annulene

• Annulenes are defined as completely

conjugated monocyclic polyenes.
• It is also defined as a cyclic hydrocarbon
with alternating single and double bonds.
• General formula: (CH)2n, Where n > 1
• Nomenclature: [No. of C atoms]+Annulene
• Examples: Cyclobutadiene, Benzene,
Cyclooctatetraene
 TYPES OF ANNULENES
• Aromatic Annulene
Cyclic, planar, fully conjugated Annulene with
(4n+2)π electrons.

• Anti-Aromatic Annulene
Cyclic, planar, fully conjugated Annulene with
(4n)π electrons.

• Non-Aromatic Annulene
Annulene that violates one or more conditions
for aromaticity.
AROMATICITY OF ANNULENES

i) [4] Annulene
• It is commonly known as Cyclobutadiene.
• Cyclic
• Planar
• Completely Conjugated
• Has (4n) π electrons. {n=1}
• Hence it is an Anti-Aromatic Annulene.
AROMATICITY OF ANNULENES

ii) [6] Annulene

• It is commonly known as Benzene.
• Cyclic
• Planar
• Completely conjugated
• Has (4n+2) π electrons. {n=1}
• Hence it is an Aromatic Annulene
AROMATICITY OF ANNULENES

iii) [8] Annulene

• Cyclic and completely conjugated
• It has (4n) π electrons. {n=2}
• It is expected to have a planar
structure and be an Anti-Aromatic
Annulene.

• But due to high angle strain, the

molecule adopts a non planar
tub shaped geometry.
• Hence it is a Non-Aromatic Annulene
AROMATICITY OF ANNULENES

iv) [10] Annulene

• Cyclic and completely conjugated
• It has (4n+2) π electrons {n=2}
• It is expected to be an Aromatic Annulene.
• But it adopts a non planar geometry in all the three
configurations.
• Hence it is a Non-Aromatic Annulene

a) All-cis [10] Annulene

• Large angle strain
• Planarity is lost
• No delocalisation of π electrons
AROMATICITY OF ANNULENES

b) mono-trans [10] Annulene

• Angle strain still persists
• Planarity is lost

c) di-trans [10] Annulene

• No angle strain
• Hydrogen atom interaction
• Planarity is lost
• If the two H atoms is replaced by a bond, we get
Aromatic Naphthalene.
AROMATICITY OF ANNULENES

v) [12] Annulene
• Cyclic
• Completely Conjugated
• Has (4n) π electrons. {n=3}
• Hydrogen atom interaction
• Planarity is lost
• Hence it is a Non-Aromatic Annulene.
AROMATICITY OF ANNULENES

vi) [14] Annulene

• Cyclic
• Planar
• Completely conjugated
• Has (4n+2) π electrons. {n=3}
• Hence it is a slightly Aromatic Annulene
• It is not that stable
AROMATICITY OF ANNULENES

vii) [16] Annulene

• Cyclic
• Completely Conjugated
• Has (4n) π electrons. {n=4}
• Alternating short and long
bond lengths
• Planarity is lost
• Hence it is a Non-Aromatic Annulene.
AROMATICITY OF ANNULENES

viii) [18] Annulene

• Cyclic
• Planar
• Completely conjugated
• Has (4n+2) π electrons. {n=4}
• Hence it is an Aromatic Annulene
• High stability
 Syllabus
Unit III Structural feature of aromatics –
Aromaticity characteristic features,
annulene, benzenoid, nonbenzenoid,
heteroaromatics, charged aromatics,
fulvenes, fulvalenes, anti aromatics and
homoaromatics.

3/24/2023 14
Aromaticity of Benzenoid Compounds

• Aromatic compounds are those compounds

which are planar, cyclic conjugated and follow
Huckel’s aromaticity rule (4n+2) π electrons
where n=0,1,2,…
• They give substitution reactions easily rather
than addition reactions and retain their
aromaticity.
• They are stable due to resonance and have
high resonance energy.
Classification
 Benzenoid
Benzenoids are a class of chemical
compounds with at least one benzene ring.
These compounds have increased stability
from resonance in the benzene rings.
Most aromatic hydrocarbons are benzenoid.
Notable counter examples are annulene,
azulene, trans-bicalicene etc
Naphthalene
Pyrene
 Pyridine

Pyridine has a conjugated system of six π

electrons that are delocalized over the ring. The
molecule is planar and, thus, follows the Hückel
criteria for aromatic systems. In contrast to
benzene, the electron density is not evenly
distributed over the ring, reflecting the negative
inductive effect of the nitrogen atom.
 Syllabus
Unit III Structural feature of aromatics –
Aromaticity characteristic features,
annulene, benzenoid, nonbenzenoid,
heteroaromatics, charged aromatics,
fulvenes, fulvalenes, anti aromatics and
homoaromatics.

3/24/2023 22
 AROMATICITY OF
NON-BENZENOID COMPOUNDS
Non- benzenoids: They exhibit aromatic
behaviour but do not contain rings with
any benzene nucleus.
They may have one or more rings fused
but none of the rings is a benzene ring.
e.g. Pyrrole
Cyclopentadienyl anion
Cyclpheptatrienyl cation

Cyclopropenyl cation
Azulene [14]- annulene
 AROMATICITY OF
NON-BENZENOID COMPOUNDS
 Azulene

It is made up from the fusion of two

aromatic ions, cyclopentadienyl anion and
cycloheptatrienyl cation.
The peripheral bonds have similar lengths
and it undergoes Friedel-Craft like
substitutions.
•
 Syllabus
Unit III Structural feature of aromatics –
Aromaticity characteristic features,
annulene, benzenoid, nonbenzenoid,
heteroaromatics, charged aromatics,
fulvenes, fulvalenes, anti aromatics and
homoaromatics.

3/24/2023 27
 Aromaticity of heteroaromatics
• Aromatic compounds which contain heteroatoms (e.g. O, N, S)
as part of the cyclic conjugated π system are
called heteroaromatics.
• Heterocyclic molecules can also participate in aromaticity.
This is evident in many biological molecules from amino acid
side chains to the Nitrogenous bases on DNA and RNA
• 4 Criteria for Determining Aromaticity
• Cyclic
• Planar
• Conjugated
• Huckel’s Rule
Heteroaromatic compounds
 Pyridine is aromatic

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 5-memebered heteroaromatic compounds

• In this compounds has one hetroatom (N,S,O) and all

are in sp2hybridization and planar
• Each atom in ring has unhybridized p orbital which is
perpendicular to ring
• They are totally had 6πe- (4 from carbon and 2 from
hetero atom) follows Huckel rule (4n+2)
 5-memebered heteroaromatic compounds

• In these compounds, 2 hetroatoms (N,S,O) are resent

and all are in sp2 hybridization and planar.
• Each atom in ring has unhybridized p orbital which is
perpendicular to ring.
• They are totally 6πe- (3 from carbon and 3 from hetero
atom) follows Huckel rule (4n+2)
 5-memebered heteroaromatic compounds

• In these compounds, 2 hetroatoms (N,S,O) are resent

and all are in sp2 hybridization and planar.
• Each atom in ring has unhybridized p orbital which is
perpendicular to ring.
• They are totally 6πe- (3 from carbon and 3 from hetero
atom) follows Huckel rule (4n+2)
 6-memebered heteroaromatic compounds

• All these compounds have hetroatom (Nitrogen) and all

are in sp2hybridization and planar.
• Each atom in the ring has unhybridized p orbital which is
perpendicular to ring.
• They are totally 6 π electrons (5 from carbon and 1 from
hetero atom) follow Huckel rule (4n+2)
 Bicyclic heteroaromatic compounds

• Each atom in sp2 hybridization and planar

• Totally 10 πe- (9 from carbon and 1 from hetero
atom) follows Huckel rule (4n+2)

Both have 10 π e-, they follow Huckel rule

(4n+2)
Non aromatic heterocyclic compounds

• A molecule that is neither aromatic nor antiaromatic.

• if any of these factors cyclic, planar, fully
conjugated does not match – the compound is
said to be nonaromatic.
Anti aromatic heterocyclic compounds
Anti aromatic heterocyclic compounds are similar to
aromatic heterocyclic compounds, but they are
• Cyclic
• Planar
• Conjugated
They obey Huckel’s Rule of 4n π electrons rule
 AROMATICITY OF
CHARGED AROMATICS
AROMATICITY OF CHARGED AROMATICS
• There are striking stability
relationships owing to aromaticity
in charged ring systems.

• The HMO energy levels that

apply to fully conjugated planar
three- to nine-membered rings.

• These energy levels are

applicable to ions as well as to the
neutral annulenes. A number of
cations and anions that are
completely conjugated planar
structures.
 Conjugated cyclic cations and anions:

• Among these species, the Hückel rule predicts aromatic stability for cyclopropenium ion (A),
cyclobutadiene dication (C), cyclobutadiene dianion (D), cyclopentadienide anion (F),
cycloheptatrienyl cation (tropylium ion, G), the dications and dianions derived from cyclooctatetraene
(I, J) and the cyclononatetraenide anion (K).

• The other species shown, which have 4n electrons, are expected to be quite unstable.

• These include cyclopropenide anion (B), cyclopentadienyl cation (E), and cycloheptatrienide (H).
 Cyclopropenium ions
The three-membered ring cation has 2 π-electrons and is surprisingly stable,
considering its ring strain. The cyclopropenyl cation is aromatic because it has an
uninterrupted ring of p orbital-bearing atoms and the cloud contains one (an odd
number) pair of delocalized electrons.

The cyclopropenyl anion is not aromatic because although it has an uninterrupted

ring of p orbital-bearing atoms, its cloud has two (an even number) pairs of electrons.
 Cyclobutadiene ions

• Forming a planar, conjugated, 4-membered ring and placing 4 π-electrons

in it creates a π-system that is energetically less stable than 2 conjugated
C=C bonds (e.g. in butadiene). Further theoretical analysis suggests that due
to its lack of aromaticity it will distort from a square structure to a
rectangular one with alternating single and double bonds (Jahn–Teller
effect).
• Derivatives of both the cyclobutadiene dication (4n+2, n=0) and the
cyclobutadiene dianion (4n+2, n=1) have been prepared and studied. The
stability is much less than that of benzene, but much more than that of
cyclobutadiene.
• Placing two charges in these small rings results in extremely high
coulombic repulsions in both the dianion and dication.
 Cyclopentadienyl ions
The cyclopentadienyl anion is aromatic, this does not necessarily imply
that it is as stable as benzene. As a carbanion, the cyclopentadienyl anion
reacts readily with electrophiles. Because this ion is aromatic, it is more
stable than the corresponding open-chain ion.
Huckel's rule predicts that the cyclopentadienyl cation, with four pi
electrons, is antiaromatic.
 Cycloheptatrienyl ions (Tropylium ions)

The Cycloheptatrienyl ion rings are a flat seven-membered

ring with seven p orbitals aligned.
The cation has six pi electrons, and the anion has eight
pi electrons.
The eight-electron system is antiaromatic .
 Cyclooctatetraene ions

• Cyclooctatetraene (COT) could be planar if there were

some stabilization energy to compensate. A planar COT
ring would have alternating double and single bonds like
benzene, but it has 8 π electrons.

• The COT dication contains 6 π electrons. This makes

it aromatic (stable).
 Cyclooctatetraene ions

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3/24/2023 47
 Cyclononatetraenyl ion

►Cyclononatetraenyl anion is a 10π aromatic system. Two

isomers of the cyclononatetraenyl anion are known:
the trans,cis,cis,cis isomer ("Pac-Man"-shaped) and the all-
cis isomer (a convex enneagon). The former is less stable and
isomerizes to the latter upon warming from –40°C to room
temperature.
►Despite the ring strain resulting from having C–C–C bond
angles of 140° instead of the ideal 120° for sp2 carbon, this
species is believed to be planar and to possess D9h symmetry.
►Cyclononatetraenyl cation is an 8π system. Computation and
experimental evidence suggest that C9H9+ is a rare example of a
ground state species that exhibits Möbius aromaticity.
 MOBIUS AROMATICITY
• A monocyclic array of orbitals in which there is
a single out-of-phase overlap (or, more
generally, an odd number of out-of-phase
overlaps) reveals the opposite pattern of
aromatic character to Hückel systems; with 4n
electrons it is stabilized (aromatic), whereas
with 4n + 2 it is destabilized (antiaromatic).
• In the excited state 4n + 2 Möbius pi-electron
systems are stabilized, and 4n systems are
destabilized. No examples of ground-state
Möbius pi systems are known, but the concept
has been applied to transition states of
pericyclic reactions.
 Syllabus
Unit III Structural feature of aromatics –
Aromaticity characteristic features,
annulene, benzenoid, nonbenzenoid,
heteroaromatics, charged aromatics,
fulvenes, fulvalenes, anti aromatics and
homoaromatics.

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 Aromaticity of Fulvenes

• Fulvene (Penta fulvene) usually refers

to the hydrocarbon (CH=CH)2C=CH2. It
is a prototype of a cross-conjugated
hydrocarbon.
• They are mainly of interest as ligand
and precursors to ligands
in coordination chemistry. They are
often yellow in color.
• Fulvene is a non-aromatic molecule,
but variation of the electron-donating/
withdrawing power of substituent exo to
the five-membered ring can drive the
system between the extremes of
aromatic and antiaromatic.
 Classification of fulvenes
• Different types of fulvenes are

• Pentafulvene
• Triafulvene
• Heptafulvene
• Nonafulvene
 Structures of fulvenes

Hepta fulvene
Tria fulvene

Penta fulvene Nona fulvene

Electronic effects in these
systems may be
envisaged by resonance
structures in which
electrons are donated
to the rings or withdrawn
by the exocyclic
substituents.
For 1n, 2o, 3n,
and 4o which have 4 or 8
π electrons in the ring this
induces antiaromatic anti-
Hückel character,
and 1o, 2n, 3o, and 4n, in
which there are 2, 6, or 10
π electrons in the ring, are
Hückel aromatic systems.
 Oxo fulvenes

If the double bond is connected with heteroatom like O,

N,……etc.

4πe- 2πe-
Antiaromatic Aromatic
 Oxo fulvenes

Since oxygen is very electronegative, it will try to drag electrons

towards it.

4πe-
Antiaromatic

2πe-
Aromatic
 AROMATICITY OF FULVALENE

• Fulvalenes are a family of molecules built from

two fully-conjugated rings, connected to one
another by an exocyclic double bond.
• The name is derived from the similarly structured
fulvenes which lack one ring.
• The parent structure of this class is pentafulvalene
which is also simply called fulvalene.
 FULVALENES
• It is of theoretical interest as one of the simplest
non-benzenoid conjugated hydrocarbons.
• Fulvalene is an unstable isomer of the more
common benzenoid aromatic compounds naphthale
ne and azulene.
• An earlier attempt at synthesis of fulvalene in
1951 by Pauson and Kealy resulted in the accidental
discovery of ferrocene.
• Its synthesis was first reported in 1958 by E. A.
Matzner. In this method, cyclopentadienyl anion is
coupled with iodine to form dihydrofulvalene.
 FULVALENES
• Examples of fulvalenes

Triapentafulvalene

Trifulvalene Pentafulvalene

Sesquifulvalene
 FULVALENES
STABILITY

• In general, the parent fulvalenes are very unstable; the

parent triafulvalene has never been synthesized.

• Stable fulvalenes can be obtained by

proper substitution or benzannulation.
• Several members should be stabilized considering a
dipolar mesomeric form.
 AROMATICITY OF FULVALENES
• The double bond can be viewed as a loose pair of electron that can
undergo resonance movement and ionization that helps the
compound aromatic
• These compounds become aromatic after breaking the double
bond outside
• Two antiaromatic unstable Two aromatic stable
TRIFULVALENE

• It undergo cleavage
in the doble bond and
form one aromatic
part and other
antiaromatic one.
• Therefore this
compound
is unstable.
PENTAFULVALENE

• It undergo cleavage
to form one aromatic
and one antiaromatic
group which is
unstable
TRIAPENTAFULVALENE

• It is also called calicene

• Here the compound
undergo cleavage to form
two aromatic part forming a
permanent dipole moment
• Hence it is a stable
compound
 SESQUIFULVALENE

• It undergo cleavage to form tropylium

cation joined to a cyclopentadienyl anion
• Both are aromatic and thus forms stable
compound
 HEPTAFULVALENE

• The compound break to form one aromatic and

other antiaromatic part.
• Therefore is unstable.
 Syllabus
Unit III Structural feature of aromatics –
Aromaticity characteristic features,
annulene, benzenoid, nonbenzenoid,
heteroaromatics, charged aromatics,
fulvenes, fulvalenes, anti aromatics and
homoaromatics.

3/24/2023 69
 Antiaromatic Compounds
Antiaromaticity is a characteristic of a cyclic
molecule with a π electron system that has higher
energy due to the presence of 4n delocalised
electrons in it.

Antiaromatic compounds are unstable and

highly reactive.
AROMATIC ANTIAROMATIC

Extra stable Extra unstable

Follows 4n+2 rule 4n pi electron

2,6,10,14,18,22... 4,8,12,16...
Cyclic Cyclic

Conjugated Conjugated

sp2 sp2

planar planar
 Examples
• 1.Cyclopentadienyl cation

• Cyclic
• Planar
• Conjugated
• 4π electrons
 2. 1,3-Cyclobutadiene

• Cyclic
• Planar
• Conjugated
• 4π electrons

Example for antiaromatic anulene

 3. Pentalene

• Cyclic
• Planar
• Conjugated
• 8π electrons
 4. Biphenylene

• Cyclic
• Planar
• Conjugated
• 12π electrons

Example for antiaromatic benzenoid compound

Examples for charged antiaromatic compounds
Examples for charged antiaromatic compounds
Antiaromatic hetero cyclic compounds
Antiaromatic fulvalenes
Cyclobutadiene is the subject of debate, with
some scientists arguing that antiaromaticity is not
a major factor contributing to its destabilization.
 HOMOAROMATICITY

• Homoaromaticity is the special case of aromaticity in

which conjugation is interrupted by a single sp3 hybridized
carbon atom.
• This concept of homoaromaticity was pioneered by Saul
Winsten
• Homoaromatic compounds are less stable due to ring strain
than planar cyclic molecule.
• Homoaromatic compounds are known to exist as cationic
and anionic species, neutral compounds are less common.
 Criterion for homoaromaticity

• cyclic
• 4n+2π electrons, satisfying Huckel’s rule
• Conjugated systems has at least 1sp3 carbon
atom
 EXAMPLES OF HOMOAROMATICITY

non-aromatic homoaromatric
Nonplanar satisfy huckels rule
 Cationic homoaromatics

• The homotropenylium cation is the most studied homoaromatic

compound

• Another well established cationic homoaromatic

compound is
 Neutral homoaromatics

• There are many classes of neutral homoaromatic

compounds although there is much debate as to
whether they truly exhibit homoaromatic character.
• One class of neutral homoaromatics are called
monohomoaromatics, one of which is
cycloheptatriene.
• Example is a 60-carbon fulleroid derivative that has a
single methylene bridge.
 Bishomoaromatics
• The best examples of neutral homoaromatics are
bishomoaromatics such as barrelene and semibullvalene.
• semibullvalene has a structure that should lend itself well to
homoaromaticity although there has been much debate
whether semibullvalene derivatives can provide a true
delocalized, ground state neutral homoaromatic compound
or not.
• To further stabilize the delocalized transition structure by
substituting semibullvalene with electron donating and
accepting groups, it has been found that the activation barrier
to this rearrangement can be lowered, but not eliminated.
 Bishomoaromatics
• The introduction of ring strain into the
molecule, aimed at destabilizing the localized
ground state structure's through the strategic
addition of cyclic annulations, a delocalized
homoaromatic ground-state structure can
indeed be achieved.
 Neutral Homoaromaticity

• The compounds best believed to exhibit neutral

homoaromaticity are boron containing compounds of
1,2-diboretane and its derivatives.
• Substituted diboretanes are shown to have a much
greater stabilization in the delocalized state over the
localized one, giving strong indications of
homoaromaticity.
• When electron-donating groups are attached to the
two boron atoms, the compound favors a classical
model with localized bonds.
 Neutral Homoaromaticity

• Homoaromatic character is best seen when

electron-withdrawing groups are bonded to the
boron atoms, causing the compound to adopt a
nonclassical, delocalized structure.
 Trishomoaromatics

• As the name suggests, trishomoaromatics are

defined as containing one additional methylene
bridge compared to bishomoaromatics, therefore
containing three of these homoconjugate bridges in
total.

• Just like semibullvalene, there is still much debate

as to the extent of the homoaromatic character of
trishomoaromatics.
 Trishomoaromatics
• While theoretically they are homoaromatic, these
compounds show a stabilization of no more than 5%
of benzene due to delocalization.
 Anionic homoaromatics
• These anionic compounds are often prepared from
their neutral parent compounds through lithium
metal reduction
• 1,2-diboretanide derivatives show strong
homoaromatic character through their three-atom
(boron, boron, carbon), two-electron bond, which
contains shorter C-B bonds than in the neutral
classical analogue.
• These 1,2-diboretanides can be expanded to larger
ring sizes with different substituents and all contain
some degree of homoaromaticity.
 Anionic homoaromatics
• Anionic homoaromaticity can also be seen in dianionic bis-
diazene compounds which contain a four-atom (four nitrogens),
six-electron center.
 Antihomoaromaticity
• Antiaromatic compounds which deviate
from Huckel's rule and contain a closed loop
of 4n π electrons, are relatively unstable.
• The bridged bicyclo[3.2.1]octa-3,6-dien-2-yl
cation contains only 4 π electrons, and is
therefore "bishomoantiaromatic”.
 Antihomoaromaticity
A substituted bicyclo[3.2.1]octa-3,6-dien-2-yl cation (the 2-(4'-
Fluorophenyl) bicyclo[3.2.1]oct-3,6-dien-2-yl cation) was also
shown to be an antiaromatic when compared to its
corresponding allyl cation, corroborated by theoretical
calculations as well as by NMR analysis.
 Benzene and Aromatic Compounds
The Basis of Hückel’s Rule
• Why does the number of  electrons determine whether a compound is
aromatic?
• The basis of aromaticity can be better understood by considering orbitals and
bonding.

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 Benzene and Aromatic Compounds

The Basis of Hückel’s Rule

• Thus far, we have used “valence bond theory” to explain
how bonds between atoms are formed.
• Valence bond theory is inadequate for describing systems
with many adjacent p orbitals that overlap, as is the case in
aromatic compounds.
• Molecular orbital (MO) theory permits a better explanation of
bonding in aromatic systems.
• MO theory describes bonds as the mathematical
combination of atomic orbitals that form a new set of orbitals
called molecular orbitals (MOs).
• A molecular orbital occupies a region of space in a molecule
where electrons are likely to be found.
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 Benzene and Aromatic Compounds

The Basis of Hückel’s Rule

• When forming molecular orbitals from atomic orbitals, keep
in mind that a set of n atomic orbitals forms n molecular
orbitals.
• If two atomic orbitals combine, two molecular orbitals are
formed.
• Recall that aromaticity is based on p orbital overlap.
• Also note that the two lobes of each p orbital are opposite in
phase, with a node of electron density at the nucleus.
• When two p orbitals combine, two molecular orbitals should
form.

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 Benzene and Aromatic Compounds

The Basis of Hückel’s Rule

• The combination of two p orbitals can be constructive—that is, with
like phases interacting—or destructive, that is, with opposite phases
interacting.

• When two p orbitals of similar phase overlap side-by-side, a 

bonding molecular orbital results.
• When two p orbitals of opposite phase overlap side-by-side, a *
3/24/2023 100
antibonding orbital results.
 Benzene and Aromatic Compounds

The Basis of Hückel’s Rule

• The * antibonding MO is higher in energy because a destabilizing
node results, which pushes nuclei apart when orbitals of opposite
phase combine.
Figure
Combination of two p orbitals
to form π and π* molecular
orbitals

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101
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 Benzene and Aromatic Compounds
The Basis of Hückel’s Rule
Consider benzene. Since each of the six carbon atoms in benzene has
a p orbital, six atomic p orbitals combine to form six  MOs.
Figure
The six molecular orbitals
To fill the MOs, the of benzene
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
3/24/2023 MOs. 104
 Benzene and Aromatic Compounds
The Inscribed Polygon Method of Predicting Aromaticity

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 Benzene and Aromatic Compounds
The Inscribed Polygon Method of Predicting Aromaticity

• This method works for all monocyclic completely conjugated systems

regardless of ring size.
• The total number of MOs always equals the number of vertices of the
polygon.
• The inscribed polygon method is consistent with Hückel's 4n + 2
rule—there is always one lowest energy bonding MO that can hold
two  electrons and the other bonding MOs come in degenerate pairs
3/24/2023 106
that can hold a total of four  electrons.
 Benzene and Aromatic Compounds

The Inscribed Polygon Method of Predicting Aromaticity

Figure
Using the inscribed polygon
method for five- and seven-
membered rings

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 Benzene and Aromatic Compounds
The Inscribed Polygon Method of Predicting Aromaticity

• For the compound to be aromatic, these MOs must be completely

filled with electrons, so the “magic numbers” for aromaticity fit
Hückel’s 4n + 2 rule.
Figure
MO patterns for cyclic,
completely conjugated systems

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 Syllabus
Unit III Structural feature of aromatics –
Aromaticity characteristic features,
annulene, benzenoid, nonbenzenoid,
heteroaromatics, charged aromatics,
fulvenes, fulvalenes, anti aromatics and
homoaromatics.

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