CH 105: Organic Chemistry

Huckel Theory For Conjugated Systems

Santosh J. Gharpure
Room No. 440
Department of Chemistry,
IIT Bombay, Powai
Mumbai 400076
e-mail: sjgharpure@chem.iitb.ac.in
sjgharpure@gmail.com
Phone: 2576 7171

Acknowledgements for lecture slides

Prof. R.B. Sunoj, IIT Bombay
Prof. Pradeepkumar P. I., IIT Bombay
Prof. K. M. Muraleedharan, IIT Madras
Prof. Peter Volhardt, UC Berkeley
Prof. J. M McBride, Yale University
Oxford University Press

Outline
Huckel Theory For Conjugated Systems
Stereochemistry
Conformational Analysis
Chemistry of Carbonyl Compounds

Text Book
Organic Chemistry : Structure and Function by Volhardt &
Schore, 5th Edition
http://bcs.whfreeman.com/vollhardtschore5e/default.asp
Additional Reading
Organic Chemistry, Clayden, Green, Warren and Wothers,
Oxford University Press
Animations
http://www.chemtube3d.com/

Course Outline and Evaluation

Organic Chemistry till Mid August (~ August 11 )
Inorganic Chemistry from Mid August to Mid-Sem
Evaluation: Organic + Inorganic (one grade)
For Organic: one exam (Quiz) of 25 Marks (It is final
exam for Organic!) Duration 2 hours
Tentative Exam Date: August 22 (to be confirmed)
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Aromaticity: Banzene

Aroma = Characteristic Odour

IN TODAYS CONTXET AROMATIC IS A MISNOMER!! 6

C6H6: How many isomers??

???

So What is Aromatic? Banzene Like Molecules

Benzene is special:

Structure:

Reactions:

Kekule suggested rapid C=C oscillation feature

What we call today as resonance

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Benzene is unusually unreactive. Does this mean

that it is also especially stable
thermodynamically? Look at H hydrogenation:

Cyclohexane

Special stability is now called aromaticity. All cyclic 6e arrangements

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are aromatic, including transition states.

Banzene: Structure
The concepts of hybridization of atomic orbitals and the
theory of resonance, developed in the 1930s, provided
the first adequate description of benzenes structure.!
The carbon skeleton is a planar regular hexagon.!
All C-C-C and H-C-C bond angles 120.!
H 120
H
sp2 -sp2
120 C
C

120
H
C
C H
C
C
109 pm
sp2 -1s
H
139 pm H

All C-C bonds 1.39

All C-H bonds 1.09

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Banzene: Structure
(a) The carbon framework with the six 2p orbitals.!
(b) Overlap of the parallel 2p orbitals forms one torus
above the plane of the ring and another below it!
this orbital represents the lowest-lying pi-bonding
molecular orbital.!

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Is Banzene UNIQUE?
How about other Annulenes?
Annulenes: Monocyclic hydrocarbons with alternating
single and double bonds

cyclobutadiene
[4]-annulene

benzene
[6]-annulene

Highly Unstable
Bonds are localized
Isolated in argon matrix

Just conjugation not

enough!

cyclooctatetraene
[8]-annulene
Not Aromatic
Tub shaped
Localized Bonds

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Huckel Theory
For Conjugated Systems

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Symmetry of objects

Picture courtesy: world of stock

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Symmetry in Nature

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Symmetry
Symmetry Elements
A geometrical entity such as a line, a plane or a
point, with respect to which one or more symmetry
operations may be carried out
1. Plane of symmetry ()
2. Center of symmetry or (inversion symmetry)-(i)
3. Axis of symmetry (C)

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CH103
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Symmetry in Molecules
3

Rotation (C)

B
F

3
F

B
F

B
F

Reflection (s)
2
1

B
F

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Molecular Symmetry

One C6 axis, Six C2 axes

One h, Six v
One i

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Orbital Symmetry
*

Symmetric along the

axis

For any bonding molecular orbital (BMO) there should be a

corresponding antibonding molecular orbital (ABMO)

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CH105
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More on sigma orbitals

(i)

(iii)

(ii)

-type overlaps contain no nodes along the internuclear axis.
Symmetric along the axis

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Types of Orbitals: Ethylene

*

*

Nonbonding orbital: e.g., pz-orbital (AO) on BH3

H
H

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Significance of Orbital Energies

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Nucleophiles have higher energy filled nonbonding orbitals

(Ready to donate electrons to suitable electrophiles)
e.g., nonbonding MO in NH3 that contains the lone pair of
electrons is responsible for the nucleophilic nature of the
molecule

Electrophiles are characterized by lower energy unfilled

nonbonding orbitals
e.g., empty nonbonding MO in BF3
Electron Rich to Electron poor

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Types of Orbitals: Formaldehyde

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In xy-plane

CO*

Empty levels

Frontier MOs
nO

Filled levels
nO

CO

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Ethylene MOs

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Ethylene shows interesting properties due to the presence

of a -bond
The C-C p-orbital is the Highest Occupied Molecular Orbital
(HOMO) of the alkene
Linear Combination of p-orbitals, leading to C-C -orbital
can be represented as,
Out of-phase combination of
p-orbitals to give a -orbital

Nodal Plane (nodes)

* orbital higher in energy
than p-orbital
Increasing
Energy of
Orbitals

2 x

-orbital lower in energy

than p-orbital
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Ethylene MOs

Increasing
Energy of
Orbitals
+

* (Antibonding
molecular orbital)

(Bonding molecular
orbital)

Total Number of -electrons = 2

Total Number of -orbitals = 2
Both electrons will occupy the lowest energy MO, i.e., BMO

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How about MOs for allyl system?

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Can we construct butadiene MOs?

3 _ 4 =

3 + 4 =

1 _ 2 =

LUMO

HOMO

1 + 2 =

LUMO is lower
in energy than
the LUMO of
ethylene
HOMO is higher
in energy than
the HOMO of
ethylene

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Butadiene MOs
Total number of p-orbitals = 4
Total number of -electrons = 4

3
4

2
1

Butadiene is
more reactive
than ethylene

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Generalizations for Acylic Polyenes

The lowest energy orbital is always symmetric with
respect to the principal mirror plane
The number of nodes increases by ONE on going from
one orbital to the next higher energy orbital
Nodes must be symmetrically located with respect to the
central mirror plane
In systems with an odd number of atoms, the
antisymmetric levels always have a node at the central
carbon atom.

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HOMO-LUMO Gap

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Extended Conjugation and Colour (E.g. 1)

If the conjugation is extended further, the gap between HOMO and LUMO
will decrease to allow the compound to absorb visible light and hence
be COLOURED.

Lycopene, the red pigment present in tomatoes and other berries

-carotene, the red pigment present in carrots and other vegetables

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Extended Conjugation and Color (E.g. 2)

The colour of the blue jeans come from the pigment indigo
O

N
H

H
N

Colourless Indigo precursor

Air
N
H

H
N

Indigo

Jeans are generally dyed by immersion in a vat of reduced indigo,

which is colourless since there is no conjugation.
When the cloth is hung up to dry, the oxygen in the air oxidizes the
pigment to indigo and the jeans turn blue.
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CH103
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Polyenes to Solids

When Number of atoms (N) in a polyene become infinitely

large, the difference between neighboring energy levels
(MO-levels) is infinitely small. But the band has a finite
width
Band

N=6

N
N=5

Q.
N=4

N=3

N=2

Is it possible to calculate
the width of the band, in
an approximate fashion?
This will help us find
overlap regions between
s and p bands
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Polyenes-to-Solids Analogies

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Approximate Analogs Between Molecular and Solid-State Terminologies

Molecular Orbital

Band Orbital

HOMO

Valence Band

LUMO

Conduction Band

HOMO-LUMO gap

Band gap

Refer: Moores law

(processor speed of cpus)
Advanced and Related Topics: Organic Semiconductors,
Organic LEDs, Conducting Polymers

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Some questions of significance

Most of the reactivities of conjugated systems (say,
butadiene, or a carbonyl compound) primarily arise due
to the -molecular orbitals.
Is it possible to estimate the energies of the -molecular
orbitals?

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Huckel MO Theory
Basic Approximations
Used for the treatment of conjugated systems
The -system is treated independently of the -framework
in planar conjugated molecules
Or -system do not interact with the -skeleton
Interactions between p orbitals located on atoms which
are not directly linked is zero
-electron approximation: -electrons move in some fixed
effective potential of framework
pi-system

Sigma-Framework

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Energies of MOs in terms of Integrals

The energy of each p-orbital before interaction is set
equal to , (Coulomb integral)
[refers to energy of an electron in the field of its own nucleus]
[can be taken as valence state ionization potential]

The interaction energy between two adjacent p

orbitals equals to (Resonance integral)

[refers to energy of i th electron in the field of j th nucleus]

[can be taken as the interaction between atomic orbitals i and j]
[energy of an electron in the field of two or more nuclei]

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CH105
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Energies of MOs

The energy of the jth MO for a linear unbranched conjugated

polyene with N p orbitals (or N number of carbon atoms) is
given by

ej = + 2 Cos

N +1

j
j = 1, 2, ,N

The energy of the jth MO for a cyclic polyene with N p orbitals

is given by

2
ej = + 2 Cos
N

j
j = 0,1, 2, ,N

Note: and are negative (attractive !) by definition

The and are not calculated as numerical values, but the
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energies are expressed in terms of these quantities

Energies of the molecular orbitals of

ethylene and butadiene by geometry

Dummy atoms at top and bottom of circle

Divide semicircle into n+1 equal arcs (parts)
Energy of the electron is given by the expression:
k is the number of the atom
along the sequence of n atoms

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Energies of MOs
For ethylene
Energy of LUMO = -

Energy of HOMO = +

For Butadiene
Energy of LUMO = - 0.62

Energy of HOMO = + 0.62

Linear polyenes
When the number of orbitals in the chain increases, the
energies will be as,
For
Highest energy MO = 2

Lowest energy MO = + 2

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Energies of MOs
Cyclic polyenes
Draw a circle of radius 2 and inscribe an N-vertex
polygon such that two vertices are in the six oclock
position. The points of contact between the circle and the
polygon defines the energy levels
- 2
Frost Diagram
- 2

+ 2

+ 2

The energy level is at the same level as that of the center

of the circle
(Note: no dummy atoms in the cyclic system!)
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Energies of MOs
Calculate the total energy of -electrons in benzene?
- 2

Total number of -electrons = 6
Total energy

= 2 * ( + 2) +

4 * ( + )

6 + 8

+ 2

If the double bonds were localized (not conjugated)!
Equivalent to three ethylenes
Total energy

= 6 * ( + )

Additional Stabilization in Benzene (fully delocalized) = 2

[What is the resonance stabilization energy in benzene?]
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Huckels Rule of Aromaticity

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Planar, fully conjugated, monocyclic systems with (4n+2)

electrons having a closed shell of electrons all in bonding orbitals
are exceptionally stable. Such compounds are said to be aromatic
Analogous systems with 4n electrons are described as antiaromatic

i
Modern definition of aromaticity:
Compounds that possesses the ability to sustain induced ring current
when subjected to magnetic field
http://nptel.ac.in/courses/IIT-MADRAS/Engineering_Chemistry_III/pdf/
1_Aromaticity.pdf
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Huckels Rule of Aromaticity

Number of electrons = 6
Satisfies Huckel rule,
where n = 1
Aromatic

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Number of electrons = 4
Where n = 1
Anti-aromatic

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Huckels Rule and Aromaticity

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The compound must have an uninterrupted cyclic -cloud of

electrons
For the -cloud to be cyclic, the molecule must be cyclic.
For the -cloud to be uninterrupted, every atom in the ring must have a p-orbital
For the -cloud to form, each p-orbital must be able to overlap with the p-orbitals on
either side of it. This means that the molecule must be planar.

E.g., 1

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 Molecular Orbitals of Benzene

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Picture from Volhardts book

CH105
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Examples for Aromatic Compounds

Phenathrene

H
H

H
H

cyclopentadienyl anion

_
_
_

H
H

[18]-annulene

Azulene

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Aromatic Heterocyclic Compounds

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Lone pair is part of the aromatic system

N
H

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CH105
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Aromatic Heterocyclic Compounds

Lone pair not involved in aromatic system

N
N

6 electrons
4n + 2 = 6, with n=1

10 electrons
4n + 2 = 10, with n=2

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CH105
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Antiaromatic Compounds

Cyclic planar molecules with conjugated 4n -electrons (where n is

an integer) are antiaromatic
Antiaromatic compounds are less stable than the open chain
counterpart
NH

A cyclic compound that does not have a continuous conjugated p orbitals are
known as nonaromatic
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e.g., 1,2-cyclohexadiene or 1,3-cyclohexadiene

Criteria for Aromaticity

The underlying criteria for aromaticity were recognized in
the early 1930s by Erich Hckel, based on molecular
orbital (MO) calculations.
To be aromatic, a compound must
Be cyclic.
Have one p orbital on each atom of the ring.
Be planar or nearly planar so that there is continuous
or nearly continuous overlap of all p orbitals of the
ring.
Have a closed loop of (4n + 2) pi electrons in the cyclic
arrangement of p orbitals.

But I dont know MO! What do I do?

Use Frost Circle

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Aromatic, Antiaromatic and Nonaromatic

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Frost Circle

Frost circle: A graphic method for determining

the relative order of pi MOs in planar, fully
conjugated monocyclic compounds.!
Inscribe in a circle a polygon of the same number of
sides as the ring to be examined such that one of the
vertices of the polygon is at the bottom of the circle.!
The relative energies of the MOs in the ring are given
by where the vertices of the polygon touch the circle.!

Those MOs!
Below the horizontal line through the center of the ring
are bonding MOs.!
on the horizontal line are nonbonding MOs.!
above the horizontal line are antibonding MOs.!
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Frost Circle
Frost circles describing the MOs for monocyclic,
planar, fully conjugated four-, five-, and sixmembered rings.!

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Antiaromaticity

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Planar cyclooctatetraene would be antiaromatic. To avoid it,

the ring goes out of plane - possible as it is a larger ring.
It is Non-aromatic.
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How about odd numbered rings?

However, remove an H (H+ or H-) and you may

have aromatic or anitaromatic behaviour!
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POLYCYCLIC AROMATIC COMPOUNDS can follow

HUCKEL 4n+2 RULE

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Effect of aromaticity on properties

Cyclopentadiene pKa is 15 where as that of
cycloheptatriene in 46.
Azulene has dipole moment of 1.8D.
Tropylium bromide is actually ioninc compound.
Pyrrole is much weaker base than pyridine.
1,2,3,4,5-penta(trifluoromethyl)cyclopentadiene is
stronger acid than nitric acid!
Ferrocene (Cp2Fe) undegoes electrophilc aromatic
substitution.
When 3-chlorocyclopropene is treated with SbCl5, it
forms a stable salt. (This chemical behavior is to be
contrasted with that of 5-chloro-1,3-cyclopentadiene,
which cannot be made to form a stable salt.)!
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But conjugate acid of heptalene is stable!!

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THANK YOU

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