The Criteria for Aromaticity

I. Structural Criteria for Aromaticity:

Four structural criteria must be satisfied for a compound to be aromatic.
[1] A molecule must be cyclic.
To be aromatic, each p orbital must overlap with p orbitals on adjacent atoms.

[2] A molecule must be planar.

All adjacent p orbitals must be aligned so that the electron density can be delocalized.

Since cyclooctatetraene is non-planar, it is not aromatic, and it undergoes addition reactions

just like those of other alkenes.

[3] A molecule must be completely conjugated.

Aromatic compounds must have a p orbital on every atom.

[4] A molecule must satisfy Hckels rule and contain a particular number of electrons.
Hckel's rule:

Benzene is aromatic and especially stable because it contains 6 electrons. Cyclobutadiene is

antiaromatic and especially unstable because it contains 4 electrons.

It is noted that Hckels rule refers to the number of electrons, not the number of atoms in a
particular ring.

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II. Energy Criteria for Aromaticity (The Basis of Hckels 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.

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.
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.

The combination of two p orbitals can be constructivethat is, with like phases
interactingor destructive, that is, with opposite phases interacting.

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When two p orbitals of similar phase overlap side-by-side, a bonding molecular orbital results
into formation.
When two p orbitals of opposite phase overlap side-by-side, a * antibonding orbital results.

When two p orbitals of similar phase overlap side-byside, a bonding molecular

3 orbital results.
When two p orbitals of opposite phase overlap side-by56
side, a * antibonding orbital results.

The * antibonding MO is higher in energy because a destabilizing node results, which pushes
nuclei apart when orbitals of opposite phase combine.

The molecular orbital description of benzene is much more complex than the two MOs formed
in Figure 17.8.
Since each of the six carbon atoms of benzene has a p orbital, six atomic p orbitals combine to
form six molecular orbitals as shown in Figure 17.9.
The six MOs are labeled 1- 6, with 1 being the lowest energy and 6 being the
highest.
The most important features of the six benzene MOs are as follows:
The larger the number of bonding interactions, the lower in energy the MO.
The larger the number of nodes, the higher in energy the MO.
The most important features of the six benzene MOs (continued):
The larger the number of bonding interactions, the lower in energy the MO.
The larger the number of nodes, the higher in energy the MO.
Three MOs are lower in energy than the starting p orbitals, making them bonding MOs,
whereas three MOs are higher in energy than the starting p orbitals, making them
antibonding MOs.
Two pairs of MOs with the same energy are called degenerate orbitals.
The highest energy orbital that contains electrons is called the highest occupied
molecular orbital (HOMO).
The lowest energy orbital that does not contain electrons is called the lowest unoccupied
molecular orbital (LUMO).

In the case of 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.

The six molecular orbitals of benzene

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III. Structural Criteria for Aromaticity:

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
Hckel'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 that can hold a total
Figure: Using the inscribed polygon method for five- and seven membered rings
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For the compound to be aromatic, these MOs must be completely filled with electrons, so the
magic numbers for aromaticity fit Hckels 4n + 2 rule.

Figure: MO patterns for cyclic, completely conjugated systems

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Fullerene: A New Form of Carbon

Diamond

Graphite

C60 Buckyball

C60 Fullerene Structure:

After considerable work, Kroto, Smalley, and Curl determined that the
structure of the C60 buckyball was a combination of 12 pentagonal and 20
hexagonal rings, forming a spheroid shape with 60 vertices for the 60 carbons.
The pentagonal rings sit at the vertices of an icosahedron such that no 2
pentagonal rings are next to each other
Curl, Kroto, and Smalley received the Nobel Prize in 1996 for their work.
The architect R. Buckminster Fuller designed a geodesic dome for the 1967
Montreal World Exhibition with the same structure; the scientists thus named
the new molecule Buckminsterfullerene, which was shortened to fullerene
when referring to the family of molecules.

Haymets Prediction
Independently, near the same time, Tony Haymet of the University of
California at Berkeley published a paper predicting the existence of a compound of
this kind, which he called footballene.
The molecule corannulene, with a similar nonplanar assembly of carbons in
pentagonal and hexagonal rings, led Haymet to predict the existence of a similar
spheroid molecule, with sixty carbons in twelve pentagons and twenty hexagons

The bonding pattern of the C60 fullerene is shown here, with yellow bonds
representing double bonds and red bonds representing single bonds.
The pentagonal rings contain only single bonds; double bonds have a shorter
bond length and lead to instability in the pentagonal ring.
The limitations on double bond locations lead to poor delocalization of electrons,
increasing the molecules reactivity.

Aromaticity of Fulerenes:
Questions
What are suitable aromaticity criteria for fullerenes?
Against which standards should the aromatic properties of fullerenes be measured?
Are there count rules similar to the Huckel rule?
Researchers have been able to increase the reactivity of fullerenes by attaching
active groups to their surfaces. Buckminsterfullerene does not exhibit
"superaromaticity": that is, the electrons in the hexagonal rings do not delocalize over
the whole molecule.
A spherical fullerene of n carbon atoms has n pi-bonding electrons, free to
delocalize. These should try to delocalize over the whole molecule. The quantum
mechanics of such an arrangement should be like one shell only of the well-known
quantum mechanical structure of a single atom, with a stable filled shell for n = 2, 8,
18, 32, 50, 72, 98, 128, etc.; i.e. twice a perfect square number; but this series does not
include 60. This 2(N + 1)2 rule (with N integer) for spherical aromaticity is the threedimensional analogue of Hckel's rule. The 10+ cation would satisfy this rule, and
should be aromatic. This has been shown to be the case using quantum chemical
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modelling, which showed the existence of strong diamagnetic sphere currents in the
cation.
As a result, C60 in water tends to pick up two more electrons and become an
anion. The nC60 described below may be the result of C60 trying to form a loose
metallic bond.

Criteria of Fullerenes Aromaticiy

Structural criteria

(or)
Crystal Structure of C60
[6,6]-bond length: 1.355 A
[5,6]-bond length: 1.467 A
Energetic criteria
Resonance Energy

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HRE (Huckel resonance energy) =

Magnetic properties of fullerenes

Long before the experimental discovery of
fullerenes, a term superaromaticity was used to describe
diamagnetic currents around a hypothetical threedimensional quasi-spherical carbon molecule having the
shape of a truncated icosahedron.
Immediately after their discovery, fullerenes were
expected to have unusual magnetic properties.

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Aromaticity is the reactivity of the certain material or molecule with other in

the different temparature.Fullerene also has aromaticity in different situations.A
spherical fullerene has pibonding electrons which are free to localize or delocalizein
different chemical siuations.According to the Huckels rule

the aromaticicty of

fullerene is three dimentional.This property can be improved and managed according

to the situation with the help of quantum chemical modelling which can empower the

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bonding. As a result, C60 in water tends to pick up two more electrons and become an
anion.

The buckminsterfullerenes, or usually just fullerenes for short, were

discovered in 1985 by a team of scientists from Rice University and the University of
Sussex, three of whom were awarded the 1996 Nobel Prize in Chemistry. They are
named for the resemblance of their alliotropic structure to the geodesic structures
devised by the scientist and architect Richard Buckminster "Bucky" Fuller. Fullerenes
are molecules of varying sizes composed entirely of carbon, which take the form of a
hollow sphere, ellipsoid, or tube.
Minute quantities of the fullerenes, in the form of C60, C70, C76, and C84
molecules, are produced in nature, hidden in soot and formed by lightning discharges
in the atmosphere.[3] Recently, Buckminsterfullerenes were found in a family of
minerals known as Shungites in Karelia, Russia.

In the final step a large polycyclic aromatic hydrocarbon consisting of 13

hexagons and three pentagons is submitted to flash vacuum pyrolysis at 1100C and
0.01 Torr. The three carbon chlorine bonds serve as free radical incubators and the ball
is stitched up in a no-doubt complex series of radical reactions. The chemical yield is
low: 0.1 to 1%. A small percentage of fullerenes is formed in any process which
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involves burning of hydrocarbons, e.g. in candle burning. The yield through a

combustion method is often above 1%. The method proposed does not provide any
advantage for synthesis of fullerenes compared to the usual combustion method, and
therefore, the organic synthesis of fullerenes remains a challenge for chemistry.

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