Molecular Orbitals: Molecular Orbital Theory ,

Wave equations LCAO methods, Bonding and

antibonding orbitals, Electronic configurations,
Aromatic character.

Orbital Symmetry: Orbital symmetry and the

chemical reaction, Electrocyclic reactions,
Cycloaddition: Diels-Alder reaction, 1, 3- Dipolar
addition, Sigmatropic rearrangement: Hydrogen
shifts, Carbon shifts.
Molecular orbital theory

The structure of molecules is best understood through quantum mechanics.

Exact quantum mechanical calculations are enormously complicated, and so
various methods of approximation have been worked out to simplify the
mathematics.
The method that is often the most useful for the organic chemist is based on
the concept of molecular orbitals: orbitals that are centered. not about
individual nuclei, but about all the nuclei in the molecule.

What are the various molecular orbitals of a molecule like?

What is their order of stability?
How are electrons distributed among them ?

Why certain molecules are aromatic?

Molecular orbital theory. Orbital Symmetry

Here We cannot learn how to make quantum mechanical calculations,

but we can see what the results of some of these calculations are, and
learn a little about how to use them.

We shall see, in a non-mathentatical way, what lies behind the Huckel (4n + 2)
rule for aromaticity.
And finally, we shall take a brief look at a recent-and absolutely fundamental-
development in chemical theory:

The application of the concept of orbital symmetry to the

understanding of organic reactions.
Wave equations Phase

Electrons show properties not only of particles but also of waves.

The wave character of electrons, and see how this is involved in chemical
bonding.
Some properties of waves in general:
vibrating strings or waves

n=3 nodes = 2

n=2 nodes = 1

n=1 nodes = 0

PHASE!
Electrons and atomic wave functions.
Three dimensional in a spherical potential  energies and probabilities of
finding an electron with given energy, orbitals.
s, p, d, f Atomic Orbitals (AOs)
phase is important!
n = 1, no nodes, lowest energy, s orbital

n = 2, one node, higher energy, p orbital

Like a string wave, an electron wave can have nodes, where the amplitude is zero.
On opposite sides of a node the amplitude has opposite signs. that is, the wave is of
opposite phases.
Molecular orbitals. LCAO method
The method of linear combination of atomic orbitals (LCAO)

Shapes and dispositions of bond orbitals are related.

in a simple way to the shapes and dispositions of
atomic orbitals.
 Bonding and antibonding orbitals
Quantum mechanics shows that linear combination of two functions gives, not
one, but two combinations and hence two molecular orbitals: a bonding orbital,
more stable than the component atomic orbitals; and an antibonding orbital, less
stable than the component orbitals.
Relative phases of lobes, and their disposition in space.
Molecular Orbitals (MOs)
Covalent bonds result from the overlap (combinations) of atomic orbitals to
produce molecular orbitals.
Molecular orbitals result from Linear Combinations of Atomic Orbitals.
LCAO  wave mechanics of MO’s
φ = atomic wave function
ψ = molecular wave function
For molecule A—B
ψ = φ A  φB
Bonding when:
a) appreciable overlap of atomic orbitals
b) energies of atomic orbitals are ~ equal
c) same symmetry
Hydrogen H2 H:H
LCAO of two AO’s  two MO’s
ψ2 = φA - φB antibonding σ* • •

one node
ψ1 = φA + φB bonding σ • •

no nodes
π – molecular orbitals

ethylene CH2=CH2 look only at π orbitals

How many AO’s in the π system? p + p two
How many MO’s result? also two
How many electrons in the π system? 2
ψ = pz  pz
 π - molecular orbitals for ethylene

C C 2 π*
E

C C  π
1

LCAOs MOs
Orbitals for Carbonyl group

Orbitals for ethylene

Orbitals for Carbonyl group
π – molecular orbitals for 1,3-butadiene?
CH2=CH—CH=CH2
How many AO’s in the π system? four
How many MO’s result? four
How many electrons in the π system? 4
 HOMO ? LUMO? At GS and ES
1,3-butadiene

Ground state Excited sate

C C C C 4


C C C C 3
E

C C C C 2

C C C C 
1
LCAOs MOs
HOMO = Highest Occupied Molecular Orbital
LUMO = Lowest Unoccupied Molecular Orbital

SYMMETRIC = Symmetry operation does not change

lobe signs
ANTISYMMETRIC = Symmetry operation inverts lobe
signs

Generic energy level ordering: σ, π, π*, σ* (for π-type

orbitals the more nodes, the higher the energy)

For linear systems, we’ve seen that this gives the highest
energy level (n–1) nodes. For hexatriene (n=6) that means
that the highest energy level will have 5 nodes.
HOMO ?
LUMO? At GS and ES
 +
ALLYL CATION CH2=CH—CH2 3 AO’s  3 MO’s 2 π e-

C C C  π*
3

E C C C 2 n

C C C  π
1

LCAOs MOs
http://www.kshitij-iitjee.com/Molecular-Orbital-Description-of-Stability/
Aromatic character. 4n+ 2 rule
Cyclopropenyl system : Configuration of pi electrons in cation, free
radical, and anion
Cyclopropenyl cation is unusually stable: 20 kcal/mole more
stable even than the allyl cation. In contrast, the cyclo- propenyl
free radical and anion are not unusually stable; indeed, the anion
seems to be particularly unstable.
For the cyclopropenyl anion in particular, with two electrons in
antibonding orbitals, simple calculations indicate no net
stabilization due to delocalization, that is, zero resonance energy.

Such cyclic molecules, in which delocalization actually leads to

destabilization, are not just non-aromatic; they are antiaromatic.
Cyclopropenyl free radical and anion are less stable
than their open-chain counterparts. Why?

Why Is Benzene More Stable than 1,3,5-Hexatriene?

Anti aromatic
Cyclopentadienyl system. Configuration of pi electrons in cation, free
radical, and anion.
Configuration of 6 pi electrons in cyclopentadienyl anion, benzene.
and cycloheptatrienyl cation.

xx
Orbital symmetry and the chemical reactions
Reaction can be controlled by orbital symmetry
Professor Fukui was co-recipient of the Nobel Prize in Chemistry in 1981
with Roald Hoffmann, for their independent investigations into the mechanisms
of chemical reactions. His prize-winning work focused on the role of frontier
orbitals in chemical reactions: specifically that molecules share loosely bonded
electrons which occupy the frontier orbitals, that is the Highest Occupied
Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital
(LUMO)

Frontier Molecular Orbital Theory

The frontier molecular orbitals of a compound are at the “frontier” of
electron occupation—the highest-energy occupied and lowest-energy
unoccupied molecular orbitals (the HOMO and LUMO). The HOMO is
logically viewed as nucleophilic or electron donating, while the LUMO is
electrophilic and electron accepting. Furthermore, both chemical reactions
and resonance can be explained by interactions (overlap) between a filled
HOMO and an empty LUMO on one or more molecules. FMO theory uses
these foundational ideas to explain the structure and reactivity of
molecules, and at least in organic chemistry, the theory has been insanely
successful.
xx
Orbital symmetry effects are observed in concerted
reactions, that is, in reactions where several bonds
are being made or broken simultaneously.
Woodward and Hoffmann formulated "rules," and
described certain reaction paths as symmetry
allowed and others as symmetry forbidden.

Woodward and Hoffmann made predictions, which have

been borne out by experiment.
Pericyclic reaction

In organic chemistry, a pericyclic reaction is a type of organic

reaction wherein the transition state of the molecule has a
cyclic geometry, the reaction progresses in a concerted fashion, and
the bond orbitals involved in the reaction overlap in a continuous
cycle at the transition state (aromatic transition structures).

Pericyclic reactions are usually rearrangement or addition reactions

A type of elementary reaction comprising concerted bond-breaking and

bondmaking involves neither homolysis nor heterolysis as described Previous
reaction mechanisms. These are called pericyclic reactions
Three Main Types of Pericyclic Reactions
Cycloadditions, electrocyclic reactions, and sigmatropic rearrangements: the last
two are both isomerization reactions.
Electrocyclic reactions
An electrocyclic reaction is typically an isomerization of a conjugated polyene in
which a new ring is formed and the molecule loses a π bond; both terminal sp 2
carbons of the π system must rotate to allow formation of the new σ bond between
them.
Electrocyclic reactions:
Δ or hv
conjugated polyene cyclic compound

The mechanism is concerted!

Electrocyclic reactions are both stereoselective and stereospecific

In the concerted electrocyclic reactions, symmetry must

be conserved for bonding to take place.
The molecular orbital involved = highest occupied
molecular orbital in the polyene. HOMO

C C C C 4


C C C C 3
E

C C C C 2 HOMO

C C C C 
1
LCAOs MOs
4n pi electrons
heat

HOMO = 
2

motion must be conrotatory for bonding

HOMO = 
2

disrotatory motion would

result in antibonding
 In a photochemical electrocyclic reaction, the important
orbital is HOMO* ( the first excited state ):

C C C C 4

 HOMO* = ψ3
C C C C 3
E

C C C C 2

C C C C 
1
LCAOs MOs
 hv

HOMO* = 
3

motion must be disrotatory for bonding

 hv

disrotatory
CH3 CH3
H3C CH3
H H
Why?
Ring Opening

heat

hv

heat
4n+2 pi electrons
 heat

trans,cis,trans - cis -5,6-dimethyl-

2,4,6-octatriene 1,3-cyclohexadiene
Trans,cis,trans-2,4,6-octatriene
Cis-5,6-dimethyl-1,3-cyclohexadiene

heat

disrotatory!
CH3 CH3
heat
H H
Thermal : Explanation with orbital symmetry
HOMO (polyene) = ? 6 AO 6 MO 6 e-

HOMO = 
3

disrotatory CH3 CH3

H H
photochemical

hv

polyene 6 AOs - 6 MO's 6 e-

photochemical HOMO*

three nodes -
HOMO* = 
4

conrotatory
 Question: Explain with drawing molecular orbital

heat cis -5,6-dimethyl-

or h 1,3-cyclohexadiene
or
trans -5,6-dimethyl-
1,3-cyclohexadiene
trans,cis,trans -
2,4,6-octatriene
Ring opening

CH3 CH3
heat

H H

cis -3,4-dimethyl- cis,trans -

cyclobutene 2,4-hexadiene

H CH3
heat

CH3 H

trans -3,4-dimethyl- trans,trans -

cyclobutene 2,4-hexadiene
Cycloadditions
Diels-Alder
diene + dienophile  cyclohexene
[ 4 + 2 ] cycloaddition
1. diene must be cis
2. syn- addition

[4+2]
+
The Diels-Alder cycloaddition is a concerted reaction:

Molecular orbital symmetry must be conserved.

 CH2=CH2
C C 2 LUMO
E

C C 
1
HOMO

LCAOs MOs

C C C C 4 CH2=CHCH=CH2
 LUMO
C C C C 3
E

C C C C 2 HOMO

C C C C 
1
LCAOs MOs
Which orbitals? thermal = HOMO + LUMO
HOMO = highest occupied molecular orbital
LUMO = lowest unoccupied molecular orbital

HOMO LUMO

LUMO HOMO

symmetry
allowed
supra-supra
[ 2 + 2 ] cycloadditions do not occur readily under thermal
conditions, but occur easily photochemically.

heat
+ No Reaction

hv
+
 thermal: LUMO + HOMO

C C 2 LUMO
E

C C  HOMO
1

LCAOs MOs

symmetry HOMO
forbidden for
supra-supra
LUMO
 photochemical = HOMO* & LUMO

C C 2 HOMO*
E

C C 
1

LCAOs MOs

symmetry HOMO*
allowed for
supra-supra
LUMO
 [4+4]
+

HOMO =  2
forbidden!

LUMO = 
3
 [4+4]
+

[4+2]
 [4+4]
+
hv

HOMO* =  3
allowed
LUMO = 
3
 So, all these observations can be explained by considering the orbitals involved in the reactions:

In this Diels-Alder reaction the reagents approach each other in a ‘face to face’ manner, i.e. so
that the p- orbitals of the p-system can combine with each other. The relevant orbitals are
shown below:

2+2 or 4+4 thermal symmetry forbidden

H H
H H
H LUMO H H LUMO
H
H H
Alkene Butadiene
H H
H H
H H HOMO H H HOMO
H H

2+2
4+4
Woodward-Hoffmann theory for prediction of the stereochemistry
of pericyclic reactions: Cycloaddition reactions. (4+2 pi)

So the following combinations can be employed in the suprafacial

cycloaddition reaction: Symmetry allowed thermally

In both cases, phases of the wave functions on the orbitals are matched so that the reagents can approach each
other in a face to face manner and also form bonds easily. 73
If, in a concerted reaction of this kind, both bonds to a
component are being formed (or broken) on the same face, the
process is said to be suprafacial.

If the bonds are being formed (or broken) on opposite faces,

the process is antarafacial.
These terms resemble the familiar ones syn and anti, but with
this difference:

• Syn and anti describe the net stereochemistry of a reaction.

• We have seen anti addition, for example, as the overall

result of a two-step mechanism.

• Suprafacial and antarafacial, in contrast, refer to actual

processes: the simultaneous making (or breaking) of two
bonds on the same face or opposite faces of a component.
Reaction takes place very easily, often
spontaneously, and at most requires moderate
application of heat.
There are several aspects to the stereochemistry
of the Diets-Alder reaction.
 Woodward-Hoffmann theory for prediction of the stereochemistry
of pericyclic reactions: Cycloaddition reactions.

Reaction takes place very easily, often spontaneously, and at most requires moderate application
of heat.
There are several aspects to the stereochemistry of the Diets-Alder reaction.

Consider the reaction of a butadiene with an alkene (the Diels-Alder reaction):

The reaction is usually heat-promoted,

but sometimes it is carried out photochemically.

More details of the Diels-Alder reaction.

1) Diene must be in the s-cis conformation: This will react: But not this:

(ends are too

s-cis s-trans far apart)

77
2) Dienophiles with electron-withdrawing groups (EWG) react faster:

Me Me
slow

O This is because the electron-

CO2Me withdrawing group reduces
OMe
the LUMO energy and
improves the overlap with the
orbitals in the diene ..
O
CO2Me
OMe
fast
OMe
CO2Me

78
3) The reaction is stereospecfic:
MeO2C
CO2Me MeO2C CO2Me
CO2Me
CO2Me

CO2Me CO2Me

Ph Ph
CO2Me
MeO2C CO2Me
heat
CO2Me
Ph Ph

Next, with respect to the alkene (dienophile) addition is clear-cut syn,

this stereospecificity is part. of the evidence that the Diels-Aider

79
5) Endo-product often favoured: Two isomers can be formed:
O O O
H
O
H
+ O O O
O H
ENDO EXO
MAJOR MINOR H
O
O
O O

In a kinetically controlled (product is fastest to form, irreversible) the ENDO is favoured but for reversible
reactions (thermodynamic control) the EXO may dominate e.g. with furan.

80
Woodward-Hofmann Rules for Cycloadditions (in short):

Thermal Photochemical
[i+j]
supra-supra supra-supra
4n forbidden allowed
supra-supra supra-supra
4n + 2 allowed forbidden

Cycloadditon reactions are controlled by the

symmetries of the HOMO of one component and the
LUMO of the other component (they must match).
82
[2 + 2] Cycloaddition. Supra,supra: geometrically possible,
but symmetry-forbidden.
Supra,antara: symmetry-allowed, but geometrically difficult.
Almost certainly, such a supra,antara process is impossible here on
geometric grounds.

But if the ring being formed is big enough, both supra,supra and
supra,antara processes are geometrically possible; in that case orbital
symmetry determines, not whether cycloaddition occurs, but how it
occurs
Problem:
Give structural formulas for the products expected from each of the following reactions.
TelI why you expect the particular products.

(a) trans,trans-2,4-hexadiene + ethylene

(b) trans-4-methyl-1 ,3-butadiene + maleic anhydride
Sigmatropic rearrangements

Migration of an atom or group with its sigma bond within

a conjugated π framework.

G G
| |
C—(C=C)n  (C=C)n—C

A concerted reaction of the type, in which a group

migrates with its sigma bond within a π framework-an
ene or a polyene-is called a sigmatropic reaction.
G [ 1,3 ] G
C C C C C C

G [ 1,5 ] G
C C C C C C C C C C

G = H, R
The migration is accompanied by a shift in pi bonds. For example:

In the designations [1,3] and [1,5] the "3" and "5" refer to the number of
the carbon to which group G is migrating (the migration terminus). The “1"
does not refer to the migration source; instead, it specifies that in both reactant
and product bonding is to the same atom (number 1) in the migrating group.
In the transition state of a sigma tropic reaction, the migrating group is
bonded to both the migration source and the migration terminus; it is the
nature of this transition state

[3,3] sigma tropic reaction, in which there is a change in position of

attachment in G as well as in the pi framework-indeed, G itself is a pi
framework.
Example [3,3] (Cope rearrangement)
HOMO [ p

[ 1,3 ]

[ 1,5 ]

[ 1,7 ]
Suprafacial migration of H

In the transition state, there is overlap between the HOMO

of one component and the HOMO of the other.
Each HOMO is singly occupied, and together they provide
a pair of electrons.

For larger pi frameworks, both supra and antara shifts should be possible on
geometric grounds, and here we would expect the stereochemistry to depend
simply on orbital symmetry
Suprafacial migration of H

[ 1,3 ] forbidden

[ 1,5 ]
allowed

[ 1,7 ]
forbidden
The facts agree with the above predictions: [I ,3] sigmatropic shifts of
hydrogen are not known, whereas [1,5] shifts are well known.

CH3 [1,5]-H CH2

CD2 CHD2

The heating of 3-deuterioindene (I) causes scrambling of the label to all three non-
aromatic positions.
We cannot account for the formation of II on the basis of [1,3] shifts: migration
of D would regenerate I; migration of H would yield only III.
Deuterium scrambling in indene via unstable intermediates IVa and lVb: a series of
[1,5] hydrogen shifts.
Migration of carbon.

Suprafacial migration of R

[ 1,3 ] allowed with inversion

of configuration

[ 1,5 ]
allowed with retention
of configuration

[ 1,7 ]
allowed with inversion
of configuration
 [1,5]

[1,3]
Conservation of molecular orbital symmetry is useful in concerted
reactions.
Electrocyclic reactions: stereochemistry, conrotatory or disrotatory
thermal HOMO (polyene)
photochemical HOMO* (polyene)
Cycloadditions: supra-supra allowed or forbidden
thermal LUMO & HOMO
photochemical LUMO & HOMO*
Sigmatropic rearrangements
suprafacial allowed or forbidden
retention or inversion of configuration