HYBRIDIZATION IN

COORDINATION
COMPOUNDS
Inner Orbital Octahedral Complexes
d2 sp3 Hybridization
What is Sp3 Hybridization?

 When bonds are formed, energy is released and the system becomes more stable. If carbon
forms 4 bonds rather than 2, twice as much energy is released and so the resulting molecule
becomes even more stable.
 There is only a small energy gap between the 2s and 2p orbitals, and so it pays the carbon to
provide a small amount of energy to promote an electron from the 2s to the empty 2p to give
4 unpaired electrons. The extra energy released when the bonds form more than
compensates for the initial input. Now the atom is said to be in an excited state. Now that
we've got 4 unpaired electrons ready for bonding.
 Now LETS take the example of methane molecule. Another problem arises. In methane all the
carbon-hydrogen bonds are identical, but our electrons are in two different kinds of orbitals.
You aren't going to get four identical bonds unless you start from four identical orbitals.
 The electrons rearrange themselves again in a process called hybridization.
 This reorganizes the electrons into four identical hybrid orbitals called sp3hybrids (because
they are made from one s orbital and three p orbitals). You should read "sp3" as "s p three" -
not as "s p cubed.
Verification through Structure:
Key Points:

 The bonds in a methane (CH4) molecule are formed by four separate but
equivalent orbitals; a single 2s and three 2p orbitals of the carbon hybridize
into four sp3 orbitals.
 In the ammonia molecule (NH3), 2s and 2p orbitals create four sp3hybrid
orbitals, one of which is occupied by a lone pair of electrons.
 In a water molecule, two sp3 hybrid orbitals are occupied by the two lone
pairs on the oxygen atom, while the other two bond with hydrogen.
sp3 Hybridization in Methane:

 In methane, 1 Carbon binds with 4 Hydrogens. The carbon atom itself has only
2 electrons available for bonding in the 2p subshell.

Carbon - Ground (normal) electron states. 1s2, 2s2, 2p1 2p1.

 In order for 4 hydrogens to bind there need to be 4 electrons available for
bonding, which cannot be achieved at the moment. The pull of a hydrogen
nucleus results in an electron being excited from the 2s subshell into the 2p
subshell, where it is available for bonding.

Carbon - An electron has been excited to the 2p orbital.

 This excitation changes the forces on the valence (bonding) electrons as the
nucleus now exerts a stronger effective core potential upon them. This and
other factors leads to the creation of a new ‘hybridized orbital’, called sp3.

Carbon - Hybridization forms sp3 orbital.

 This leaves 4 valence electrons which will each overlap with the s orbital of a
Hydrogen to form a σ (sigma) bond. These hydrogens space themselves as far apart as
possible, leading to the tetrahedral structure of methane.

3D animation of methane. Produced on ChemSketch.

 . Each of the bonds in the image above are σ-bonds.

Methane Hybridization. Shows the S orbits of H overlapping with sp3

orbitals of C. Note 2 electrons in each bond, one from carbon and one
from hydrogen. Image by K. Aainsqatsi, released into public domain.
 Ethane:
 Ethane can form by replacing one of the hydrogen atoms in CH4 with another
sp3 hybridized carbon fragment.
 If lone electron pairs are present on the central atom, that can occupy one or
more of the sp3 orbitals. For example, in the ammonia molecule, the fourth
of the sp3 hybrid orbitals on the nitrogen contains the two remaining outer-
shell electrons, which form a non-bonding lone pair.
 In the water molecule, the oxygen atom can form four sp3 orbitals. Two of
these are occupied by the two lone pairs on the oxygen atom, while the other
two are used for bonding. The observed H-O-H bond angle in water (104.5°) is
less than the tetrahedral angle (109.5°); one explanation for this is that the
non-bonding electrons tend to remain closer to the central atom and thus
exert greater repulsion on the other orbitals, pushing the two bonding orbitals
closer together.
Phosphorus Pentachloride(PCl5)
 It involves mixing of one ‘s’ orbital, three ‘p’ orbital’s and one ‘d’ orbital of
equal energy to give a new hybrid orbital known as sp3d hybridized.
 The mixture of s, p and d orbital’s forms trigonal bipyramidal symmetry.