Organic Chemistry

Molecular Orbitals
and Hybridisation
Molecular orbitals
Orbitals can be used to explain bonding between
atoms. Atomic orbitals are the volume of space that
the electrons of an atom are likely to be found in.

H H

1s atomic orbitals of hydrogen

The atomic orbitals containing the valence electrons

(outer electrons) are the ones that are important to us.
When atomic orbitals overlap, they combine to form
molecular orbitals.

In the case of hydrogen, the overlap of two 1s atomic

orbitals results in the formation of a σ (sigma)
molecular orbital.

H H H H

σ molecular
1s atomic orbitalsorbital
of hydrogen

σ bonds
This are covalent
molecular orbital bonds
is moreformed
stablebetween
than eachatoms
of the
when end-on
separate overlap
atomic of orbitals
orbitals occurs. to the shape
and contributes
of the molecule.
Molecular
The molecular
orbitals
orbital
encompass
formed isthe
a lower
wholeenergy
molecule
arrangement
and are not simply
than the
found
separate
between
atomic
atoms
orbitals.
inside a
molecule.
Increasing energy

1s 1s

σ
H H

H H
Bonding continuum
The shape of the molecular orbital formed from
overlapping atomic orbitals will govern the type of
intermolecular bonding that is observed.
Non-polar (pure) covalent bonds
Non-polar covalent bonds or pure covalent bonds are
formed between two atoms of the same element, or
two atoms with a very low difference in
electronegativity.

The molecular orbital formed from overlapping atomic

orbitals is symmetrical around a mid-point where the
bonding electrons are most likely to be found.
Non-polar (pure) covalent bonds
Example: fluorine
The overlap of two 2p orbitals results in the formation
of a σ orbital.

F + F
2p atomic orbital 2p atomic orbital
σ molecular orbital
Non-polar (pure) covalent bonds
Example: fluorine
The overlap of two 2p orbitals results in the formation
of a σ orbital.

F + F
2p atomic orbital 2p atomic orbital

F F
σ molecular orbital
In a fluorine molecule, or any non-polar covalent bond,
the σ bonding orbital is symmetrical.
Polar covalent bonds
Since oxygen
When there is is more difference
a large electronegative
betweenthanthe
hydrogen,
the molecular orbital
electronegativities of formed
the two will be asymmetrical,
elements with
involved in the
the bonding
bond, electrons
the bonding more likely
molecular to will
orbital be found
be around
the δ– oxygen atom.
asymmetrical.

Example: water δ–

O δ+
δ+

H H
Ionic bonds
When ionic bonds form, there is extreme asymmetry
and the bonding molecular orbital is almost entirely
around one atom.
Hybridisation
In its ground state, an isolated atom of carbon has the
electron arrangement 1s2 2s2 2p2.
1s 2s 2p
H

Why then, if there are

C
only two unpaired
H
H electrons, do carbon
atoms form four
H covalent bonds?
Hybridisation
The shapes of the atomic orbitals involved cannot
explain the bonding observed in compounds such as
alkanes.
z 1s 2s
z 2p
y y

z
1s orbital z 2s orbital z
y y y

2px orbital 2py orbital 2pz orbital

Hybrid theory assumes that the 2s and 2p orbitals of
carbon atoms combine (or mix) to form four
degenerate orbitals (i.e. orbitals of equal energy)
Increasing energy

2p
hybridised orbitals

The hybrid orbitals formed

from one s orbital and
2s three p orbitals are called
sp3 orbitals.
 an sp3 hybridised orbital

The sp3 orbitals formed are all half-filled, with the

electron far more likely to be found in the larger lobe.

Since electrons repel each

other, the four sp3 hybridised
orbitals surrounding a
central carbon atom result in
a familiar tetrahedral shape,
with a maximum possible
angle between each orbital
of 109.5°.
Alkanes
In methane, all four hybrid orbitals are used to form σ
bonds between the central carbon atom and hydrogen
atoms.

C
H
H
H
Alkanes
σ bonds are covalent
Carbon-to-carbon single bonds
bonds in alkanes
formed result from
by end-on
overlapping sp3atomic
overlap of two orbitals forming
orbitals σ bonds.
and since σ bonds must
lie along the line joining both atoms, there will be free
rotation around these orbitals.
H H

C C
H H
σ bond

H H
Alkenes
How can we explain the existence of double bonds as
observed in alkenes?

H H H
H
H C C H C C
H H H H

As with alkanes, bonding in alkenes is due to

hybridisation.
As
Thiswith alkanes,
results in theanformation
electron of
from thehybrid
three 2s shell is
orbitals,
promoted to the empty
with one remaining 2p orbital.2p orbital.
unhybridised

single unhybridised
2p orbital
Increasing energy

2p

hybridised orbitals

The hybrid orbitals formed

from one s orbital and two p
2s
orbitals are called sp2
orbitals.
The three sp2 orbitals repel each other, resulting in a
bond angle of 120° between them.

The hybrid orbitals are responsible for overlapping to

form σ bonds joining their central carbon atoms to
both carbon and hydrogen.

sp2 orbitals
The unhybridised p orbitals are perpendicular to the
plane of the molecule.
unhybridised
2p orbitals

H H
σ bonds C C σ bonds
H H
σ bond

The p orbitals of the carbon atoms are parallel and

close enough to overlap sideways.
This sideways overlap between the 2p orbitals
produces a new molecular orbital between the two
carbon atoms.

A π new
This bondorbital
is a covalent
is calledbond formed
a pi (π) by
orbital
theorsideways
more commonly aπ
overlap of two parallel
bond.
atomic orbitals.
σ and π bonds
Looking at information comparing σ and π bonds, we
can see that double bonds are stronger than single
bonds, but not twice as strong. This is because the
sideways overlap (π bond) is weaker than the end-on
overlap (σ bond).
Bonding Mean
Bond type orbitals Bond length bond enthalpy
present
C C 1σ 154 pm 370 kJ mol–1

C C 1σ+1π 134 pm 602 kJ mol–1

C C 1σ+2π 121 pm 835 kJ mol–1

Aromatic hydrocarbons
Aromatic compounds differ to other hydrocarbons as
they contain delocalised electrons.
Example: benzene (C6H6)
H Chemists initially represented
a molecule of benzene as
H C H
C C
shown here.
However, contrary to what
C C
H H
might be expected from this
C
structure, benzene is a very
H stable, saturated structure
that does not undergo
addition reactions.
This model does not explain why all the bonds in
benzene can be observed to be the same length, not
three longer single bonds and three shorter double
bonds.

In benzene, each carbon

atom has used three of its
H
four valence electrons to form
H C H σ bonds. The fourth electron
C C of each carbon atom is
delocalised over the entire
H
C C
H
ring, not involved in π
C
bonding.
H
The σ bonding can be described as existing between
six sp2 hybridised orbitals.

There are six C–C σ bonds in the molecule and so

each carbon atom has two σ bonds to adjacent
carbon atoms.

Every carbon atom also has a σ bond to a hydrogen.

This results in a planar molecule with the unfilled 2p
orbital of each carbon atom above and below the
plane of the molecule.

H H
C C

H C C H

C C
H H
These 2p orbitals all combine to form a set of
delocalised π molecular orbitals above and below the
plane of the molecule.

H H
C C

H C C H

C C
H H

The structure of benzene is drawn as shown

to represent the delocalised electron clouds.
A substituted benzene ring is called a phenyl group
(C6H5) and can be represented: R

Many medicines, antiseptics, drugs and other useful

products contain aromatic rings.

CH3 OH

O2N NO2 Cl Cl

NO2 Cl

Trinitrotoluene Trichlorophenol
(TNT) (TCP)