Application of CFT

Colour in Complex compounds:

The color in coordination complexes is the consequence of splitting of d orbitals.
Partially filled d orbitals absorb radiations in the visible region of the spectrum so as to
make d electrons transit from lower energy level to the higher one. Color of the
complex is light reflected by the complex which is actually complementary to the light
absorbed by the complex. Color of the complex depends on the nature of central
metal ion present in it along with its oxidation state and nature of the ligands. The
strength of crystal field is different for different ligands therefore diverse colors
can be seen. For a given metal ion, weak field ligands results in the complex of lower Δ,
that absorb light of longer wavelength. Opposite to this, strong field ligands resulting
in the complex with larger Δ absorb light of shorter wavelength λ. Other factors such
as electron-electron repulsion and Jahn-Teller effects) also changes the energy
difference of ground and excited states.

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Colour in Complex compounds (contd.)
Most transitions that occur in the colored metal complexes are either d–d
transitions or charge transfer transitions.
d-d Transitions
In a d–d transition, an electron in lower energy d orbital of the metal ion is excited by
a photon to higher d orbital. In centrosymmetric complexes, d-d transitions are
forbidden by the Laporte rule which states that, transitions within a given set of p or
d orbitals are forbidden . However, if the center of symmetry is disrupted, forbidden
transitions are allowed. An asymmetrical vibration of a molecule results in vibronic
transitions. For example in an octahedral complex of manganese (II) has d5
configuration having five electrons with parallel spin, the color of complex is weaker
than the complex with spin-allowed transitions. Tetrahedral complexes have more
intense color due to possible mixing of the d and p in absence of a center of
symmetry. Therefore, transitions are not pure d-d transitions.
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Magnetic Properties of Coordination Compounds

[Co(NH3)6]3+ and [CoF6]3-,

In both the complex , Central metal ion Co in +3 oxidation state

the complex with NH3 as ligand
forms a low spin diamagnetic complex (where all the electrons are paired up) whereas the
complex with F- as ligand form high spin complex

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Magnetic Properties of Coordination Compounds (contd.)

Magnetic moment represented by ‘μ’ can be measured from spin only formula that assumes
the magnetic moment arises from the unpaired electron spin. This formula works well for the
first transition series of the metal ion.
μs = [n(n+2) ]1/2
Where n = number of unpaired electrons
In the case of metals in second and third transition series, this formula is not applicable
because
there we also have large contributions from the angular orbital moment along with the spin
motion.
Since the complex Co(NH3)6]3+ is diamagnetic in nature thus, its magnetic moment is zero,
but for the complex [CoF6]3- it can be calculated as follows.
μs = [n(n+2) ]1/2
n = number of unpaired electrons
For, [CoF6]3-
n = 4, since it is having 4 unpaired electrons
μs = [4(4+2)]1/2
= 4.90 BM

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Limitations of CFT
1.The CFT ignores the attractive forces between the d- electrons of the metal ion
and nuclear charge on the ligand atom. Therefore all properties are dependent
upon the ligand orbital and their interactions with metal orbitals are not explained.
2.In CFT model partial covalencey of metal-ligand bonds are not taken into
consideration. According to CFT metal – ligands bonding is purely electrostatic.
Which is not so true.
3.In CFT only d- electrons of the metal ion are considered the other orbitals such
as s, px, py, pz are not taken into consideration.
4.In CFT π orbitals of ligand are not considered. Therefore it cannot explain any
properties related to ligand orbitals and their interaction with metal orbitals.
5.CFT mainly affected by spectra chemical series , which is as below:
I– < Br– < Cl– < F– < OH– < H2O < NH3 < CO etc.
a. As a ligand are assumed to be point charges, it is expected that the ionic ligand
should have greater splitting effect. However actually they found to be at lower end
of the spectrochemical series.
b. Though OH– in the spectrochemical series lies below H2O and NH3 , yet it
produces greater splitting effect.
c. CFT is unable to explain the relative strength of ligands.
6. The theory rules out the possibility of having p bonding (no information about π
bond formation in ligand). This is a serious drawback because p bonding is found in
many complexes.
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Distortions in Octahedral Geometry (John-Teller Distortion)

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 John-Teller Theorem
Theorem: In a nonlinear molecule, if degenerate orbitals are asymmetrically
occupied, a distortion will occur to remove the degeneracy.
(or)
In an electronically degenerate state, a nonlinear molecule undergoes distortion to
remove the degeneracy by lowering the symmetry and thus by lowering the energy.
What is electronically degenerate state?
An electronically degenerate state represents the availability of more than one degenerate
orbitals for an electron. In this condition the degenerate orbitals are asymmetrically occupied.
E.g. In octahedral symmetry, the d1 configuration is said to be electronically degenerate
since three t2g orbitals with same energy are available for the electron to occupy. In this
condition, the degenerate orbitals are also said to be asymmetrically occupied by electrons.
Whereas the d3 configuration in octahedral geometry is non-degenerate and symmetric. It is
not possible to put two electrons in one orbital, which is against of Hund's rule of maximum
multiplicity.

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In the electronically degenerate state, the orbitals are said to be asymmetrically
occupied and get more energy. Therefore the system tries to get rid of this extra
energy by lowering the overall symmetry of the molecule i.e., undergoing distortion,
which is otherwise known as Jahn Teller distortion.

Condition for different types of Distortions

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 Jahn-Teller Distortion in d9 Complexes

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John-Teller Distortion in Elongated Distorted Cu2+ complexes
 Metal-Ligand bond distance along Z-axis is more
 d-orbitals a having z-component (dyz, dzx and dz2 ) experience less repulsion.
 d-orbitals in xy plane (dxy and dx2-y2 ) experience more repulsion.

Order of energy of splitted d-orbitals (dyz=dzx) < dxy < dz2< dx2-y2

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John-Teller Distortion in Compressed distorted Cu2+ complexes
 Metal-Ligand bond distance along Z-axis isless
 d-orbitals a having z-component (dyz, dzx and dz2 ) experience more repulsion.
 d-orbitals in xy plane (dxy and dx2-y2 ) experience less repulsion.

Order of energy of splitted d-orbitals dxy < (dyz=dzx) < dx2-y2 < dz2

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John-Teller stabilization Energy for distorted Octahedral complexes
John-Teller stabilization Energy for Elongated Octahedral complexes:
CFSE due to distortion=
Energy of distorted complex (E2) – Energy of complex without distortion (E1)
E1= 6 (-0.4∆0)+3 (0.6∆0) = -0.6 ∆o
E2= 4( 0.4∆o – δ2/3) +2 (-0.4∆o+2δ2/3)+2 (0.6 ∆0 – δ1/2)+1 (0.6∆o+δ1/2)
E2= -0.6 ∆o-δ1/2
John-Teller stabilization Energy for Compressed Octahedral complexes:
CFSE due to distortion=
Energy of distorted complex (E2) – Energy of complex without distortion (E1)
E1= 6 (-0.4∆0)+3 (0.6∆0) = -0.6 ∆o
E2= 4( 0.4∆o – 2δ2/3) +2 (-0.4∆o+δ2/3)+2 (0.6 ∆0 – δ1/2)+1 (0.6∆o+δ1/2)
E2= -0.6 ∆o-δ1/2

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