Crystal Field Theory

The bonding in coordination complexes was first explained with the help of valence bond theory
(VBT) developed by Linus Pauling. Though many observed properties of coordination complexes can
be explained by VBT, it still has following limitations
1. The theory does not explain the colour of the complex
2. The spin only magnetic moments can easily be explained by the theory but it does not consider
the other components of magnetic moments.
3. Moreover, it does not provide a quantitative explanation as to why certain complexes are inner
orbital complexes and the others are outer orbital complexes for the same metal. For example,
[Co(NH3)6]3+ is diamagnetic whereas [CoF6]3- is paramagnetic.

Later chemists used crystal field theory (CFT), developed by Hans Bethe and John Hasbrouck
van Vleck, to explains many important properties of transition-metal complexes, including their
colours, magnetism, structures, stability, and reactivity.

Assumptions of CFT
1. The ligands are treated as point charges.
2. The interaction between the metal ion and the ligand is assumed to be purely electrostatic (ionic) in
nature.

Splitting of d-orbitals in octahedral crystal field

CFT focuses on the interaction of the five (n − 1)d orbitals with ligands arranged in a regular array
around a transition-metal ion. We will focus on the application of CFT to octahedral complexes. Let
us visualize how the energies of the d orbitals of a transition-metal ion are affected by an octahedral
arrangement of six negative charges. Initially five (n − 1)d orbitals are degenerate (have the same
energy). Initially, the attraction between central metal ion and ligands (negatively charged anions or
nucleophiles) will lower the energy of the system. When metal ion and ligands come close to each
other, due to repulsive electrostatic interactions between ligand charges or dipole and electrons in the
d orbitals, energy of the system increases slightly but five d orbitals still remain degenerate (barry
centre ). At equilibrium bond distance this repulsive interaction is not same for all d-orbitals.
Octahedral coordination results when ligands are placed in the centres of cube faces. In an octahedron
the d orbitals can be divided into two groups: dx2−y2 and dz2 (lobes of these two orbitals are placed
along the x, y and z axis and directly interact with ligands) and dxy, dxz, and dyz (lobes of these three
orbitals are placed in between the x, y and z axis and interact with ligands with an angle of 45).
z

x
Now consider the effect of the ligands on the energies of the d-orbitals in octahedral coordination,
with the dyz and dz2 orbitals as examples (two ligands along z-axis are only considered for
simplicity). An electron in the dyz orbital can approach the ligand to within a distance of a/2, where a
is the cube edge length. However, an electron in dz2 interacts directly with ligands (head on). This
means that the dz2 orbital is higher in energy due more repulsion than the dyz orbital. Thus the dz2 and
dx2−y2 orbitals point directly at the six negative charges located on the x, y, and z axes. Consequently,
the energy of an electron in these two orbitals (collectively known as eg orbitals) will be greater than it
will be for a spherical distribution of negative charge (at barry centre) because of increased
electrostatic repulsions. In contrast, the other three d orbitals (dxy, dxz, and dyz, collectively called the
t2g orbitals) are all oriented at a 45° angle to the coordinate axes, so they point between the six
negative charges. The energy of an electron in any of these three orbitals is lower than the energy for
a spherical distribution of negative charge (at barry centre).

Crystal Field Stabilisation Energies (CFSE)

The extra stabilization energy that is gained by a coordination complex due to crystal field splitting is
known as CFSE. CFSE is  10% of total stabilization energy of the system but controls all the
properties of the system.
The splitting in an octahedral complex (Oh)

t2g where t means triply degenerate

g comes from Latin word gerade
meaning symmetric
g notation is only applicable for
centrosymmetric field like octahedral (in
octahedral geometry an inversion centre
present on central metal ion)

eg where e means doubly degenerate

Degenerate means orbitals having same
energy

Electronic
Total d-electrons CFSE*
configuration
d1 t2g1 eg0 -0.4 Δo or -4 Dqo
d2 t2g2 eg0 -0.8 Δo or -8 Dqo
d3 t2g3 eg0 -1.2 Δo or -12 Dqo
For d4, the fourth electron will either occupy higher energy eg orbital or lower energy t2g orbital
depending on the nature of ligand (weak field or strong field). If the fourth electron occupies eg
orbital then the complex is known as high spin (ligand is weak field) and if the fourth electron
occupies t2g orbital then the complex is known as low spin (ligand is strong field). If the electron
occupies higher energy eg orbital (for high spin complex) then the system will destabilize by Δo
amount of energy. Whereas occupancy of t2g orbital required P (pairing) energy. Thus if Δo  P (in
case of weak field ligand) the electron will occupy eg orbital. When Δo  P (in case of strong field
ligand) the electron will occupy t2g orbital. So for d4, d5, d6 and d7 two different electron
configurations are possible.
t2g3eg1 -0.6 Δo or -6 Dqo (high spin)
d4
t2g4eg0 -1.6 Δo+P or -16 Dqo+P (low spin)
t2g3eg2 0 Δo or 0 Dqo (high spin)
d5
t2g5eg0 -2.0 Δo+2P or -20 Dqo+2P (low spin)
t2g4eg2 -0.4 Δo+P or 4 Dqo+P (high spin)
d6
t2g6eg0 -2.4 Δo+3P or -24 Dqo+3P (low spin)
t2g5eg2 -0.8 Δo+2P or -8 Dqo+2P (high spin)
d7
t2g6eg1 -2.4 Δo+3P or -24 Dqo+3P (low spin)
d8 t2g6eg2 -1.2 Δo+3P or -12 Dqo+3P
d9 t2g6eg3 -0.6 Δo+4P or -6 Dqo+4P
* Ignoring any previous pairing present in d-orbitals
The splitting in a tetrahedral complex (Td)

Only weak field ligands form tetrahedral complexes (10 Dqt or Δt is always < P, pairing
energy). As a weak field ligand can form both octahedral high-spin complex and tetrahedral
complex, in case of same weak field ligand Δt = 4/9Δo.

Total d-electrons Electronic configuration CFSE

1 1 0
d e t2 -0.6 Δt or -6 Dqt
d2 e2 t20 -1.2 Δt or -12 Dqt
d3 e2 t21 -0.8 Δt or -8 Dqt
d4 e2 t22 -0.4 Δt or -4 Dqt
d5 e2 t23 0
d6 e3 t23 -0.6 Δt + P or -6 Dqt +P
7 4 3
d e t2 -1.2 Δt + 2P or -12 Dqt + 2P
d8 e4 t24 -0.8 Δt + 3P or -4 Dqt +3P
d9 e4 t25 -0.4 Δt + 4P or -4 Dqt +4P
* Ignoring any previous pairing present in d-orbitals

Splitting in tetrahedral is reverse of octahedral. Why?

Octahedron Tetrahedron
A cube, an octahedron, and a tetrahedron are related geometrically. Octahedral coordination
results when ligands are placed in the centres of cube faces. Tetrahedral coordination results
when ligands are placed on alternate corners of a cube.

Now consider the effect of the ligands on the energies of the d-orbitals in octahedral
coordination, with the dyz and dz2 orbitals as examples (two ligands along z-axis are only
considered for simplicity). An electron in the dyz orbital can approach the ligand to within a
distance of a/2, where a is the cube edge length. However, an electron in dz2 interacts directly
with ligands (head on). This means that the dz2 orbital is higher in energy due more repulsion
than the dyz orbital.

a2/2

In a tetrahedral complex, an electron in the dyz orbital can approach the ligand to within a
distance of a/2 (with an angle of 35.27). However, an electron in dz2 only approaches the
ligands at a distance of a2/2 (with an angle of 54.47), a distance 1.414 times as long as the
distance in the dyz case. This means that the dz2 orbital is lower in energy than the dyz orbital,
exactly the opposite case as in octahedral coordination.
 Jahn-Teller Distortion
The Jahn–Teller theorem essentially states that any non-linear molecule with a spatially
degenerate electronic ground state will undergo a geometrical distortion that removes that
degeneracy, because the distortion lowers the overall energy of the species.

The Jahn–Teller effect is very common in octahedral complexes of the transition

metals.

 In a regular octahedral six M-L bonds are same.

 In distorted octahedral geometry bonds along z-axis either will be compressed or will be
elongated.
 This type of distortion in octahedral complexes is known as Tetragonal Distortion.
 If compression along z axis occurred it is known as z-in distortion and in case of
elongation along z-axis is known as z-out distortion.
 In case of z-in distortion all d-orbital having z component (dxz, dyz and dz2) will
undergo slight destabilization and dxy and dx2-y2 will stabilize slightly.
 In case of z-out distortion all d-orbital having z component (dxz, dyz and dz2) will
undergo slight stabilization and dxy and dx2-y2 will destabilize slightly.
 The distortion in eg orbitals is higher than t2g orbitals
 From above diagram it is clear that for d1 or t2g1 configuration a compressed
geometry can be predicted as single d-electron will occupy dxy orbital and system
will stabilize by -2/32 amount of energy.
 For d2 or t2g2 configuration an elongated geometry can be predicted as two d-
electrons will occupy dxz and dyz orbitals and system will stabilize by (2-1/32) = -
2/32 amount of energy.
  For d3 or t2g3 configuration, there will be no distortion as (dxz, dyz)2dxy1 electronic
configuration for z-out or dxy1(dxz, dyz)2 electronic configuration for z-in will not
produce any extra stabilization energy.
 Likewise t2g4, t2g5 configurations will give distorted geometry but t2g6 will not.
 Complexes with eg1 and eg3 configuration also show distortion.
Predicts the distortion in following electronic configurations

t2g3 eg0, t2g4eg0, t2g3eg2, t2g5eg0, t2g4eg2, t2g6eg0, t2g5eg2, t2g6eg2, t2g6eg1, t2g6eg3 t2g3eg1

Predict whether following compounds will undergo tetragonal distortion or Jahn-Teller

distortion

TiCl63, [Ti(H2O)6]2+, [Fe(H2O)6]2+, [Fe(CN)6]4-, [Fe(H2O)6]3+, [Fe(CN)6]3-, [Cr(H2O)6]3+,

[Cu(H2O)6]2+

Square planar geometry, if we remove two ligands along z-axis in an octahedron we get
square planar
Spin-Crossover Phenomenon and Spin-Crossover Complexes

Coordination compounds of transition-metal ions may, under certain conditions, exhibit a

switching phenomenon, whereby the central metal ion changes the spin state (high-spin (HS)
to Low-spin (LS)) upon a change of temperature, application of pressure, irradiation with
light, or in a magnetic field. This phenomenon is known as spin transition (ST) or spin
crossover (SCO). The change of spin state is accompanied by a change of electronic structure
of the central ion and the complex molecule on the whole, which changes markedly the
physical and chemical properties of the substance. Most spectacular is the change of
magnetic behaviour and colour, which has made such SCO substances very attractive
because of their potential for practical applications, e.g., as switching devices and sensors.
The SCO phenomenon most widely observed in six-coordinate first-row transition
metal complexes with d4–d7 configurations. As we previously seen that metal ions with d4–d7
configurations can form both high-spin (HS) and low-spin (LS) complexes depending upon
the ligand field strength. As we know when Δo  P (in case of weak field ligand), a HS
complex forms. Whereas Δo  P (in case of strong field ligand), a LS complex forms. Now
consider a ligand for which Δo  P, then HS LS equilibrium exists ie. mean that
particular

Consider Fe3+ complex with H2O and CN ligands:

H2O is weak field ligand and will form HS complex, [Fe(H2O)6]3+ with t2g3eg2 electronic
configuration.
CN is strong field ligand and will form LS complex, [Fe(CN)6]3 with t2g5eg0 electronic
configuration.
Now consider an N, N-diethyldithiocarbamate (Et2dtc) ligand, the ligand field strength of
Et2dtc is comparable with pairing energy in Fe3+ ion and thus Fe(Et2dtc)3 is a SCO complex.
The above complex exists as a HS complex at room temperature and LS complex at low
temperature.

Many Fe(II) complexes are known to exhibit SCO behaviour as given below

[Fe(btz)2(NCS)2], [Fe(phen)2(NCS)2] and [Fe(dppz)2(NCS)2]

(Where btz = 2,2'-bi-4,5-dihydrothiazine, phen = 1,10-phenanthroline and dppz =

dipyrido[3,2-a:2′3′-c]phenazine)

These complexes show diamagnetic behaviour at low temperature (due to LS configuration

t2g6eg0) and four electron paramagnetism (due to HS configuration t2g4eg2). The variable
temperature magnetic behaviour of these complexes are given below
Temperature dependence of MT for [Fe(btz)2(NCS)2], [Fe(phen)2(NCS)2] and
[Fe(dppz)2(NCS)2] (M = molar magnetic susceptibility and T = temperature)

Octahedral vs. Tetrahedral

As discussed previously a weak field ligand can form both octahedral high-spin complex and
tetrahedral complex, such as [CoCl4]2 and [NiCl6]4. It is noteworthy that same chloride
ligand form tetrahedral complex with Co(II) but prefers octahedral complex with Ni(II).
Why?

Whether a weak field ligand will prefer Oh or Td geometry for particular metal ion depends on
two competing factor,
(i) Formation of octahedral complex will produce more CFSE as we know Δt = 4/9Δo

(ii) Metal ion in an octahedral complex accommodates six ligands around itself, whereas in
tetrahedral complex there is only four ligand. Thus six ligand in Oh produce more coulombic
repulsion as L-M-L bond angle is 90. But in Td complex coulombic repulsion is less
compared to Oh complex due to greater L-M-L bond angle of 109.5. Higher coulombic
repulsion destabilize the system.
So, if higher coulombic repulsion is compensated by CFSE for Oh complex then octahedral
complex is expected. Whereas if CFSE for Oh complex cannot compensate coulombic
repulsion then tetrahedral geometry is preferred.
To determine whether CFSE for Oh geometry is sufficient to compensate coulombic repulsion
or not we required to calculate Octahedral Site Selection Energy or Octahedral Site
Stabilization Energy (OSSE).
Let us take example of Ni(II) and chloride ligand to show the calculation of OSSE:

Ni(II) and chloride can form both tetrahedral [NiCl4]2 or octahedral [NiCl6]4, but which one
is preferred?

Calculate CFSE for octahedral [NiCl6]4

Ni(II), d8 system, electronic configuration in octahedral is t2g6eg2 and CFSE is -1.2 Δo+3P.
Then calculate CFSE for tetrahedral [NiCl4]2
Electronic configuration in tetrahedral is e4 t24 and CFSE is -0.8 Δt + 3P.
Now covert CFSE for tetrahedral geometry to CFSE for octahedral geometry:

Δo = -0.8 Δt  4/9 (as only 4/9 of what we gain for the octahedral case)
= -0.355 Δo
OSSE = [-1.2 – (-0.355)] Δo
= -0.844 Δo
OSSE of -0.8444 Δo is sufficient for compensation of coulombic repulsion in octahedral
geometry. Thus octahedral geometry is more preferred for Ni(II) in presence of weak field
like chloride. More negative the OSSE more preference for octahedral geometry.

Let us repeat the calculation for Co(II) and chloride ligand

Calculate CFSE for octahedral [CoCl6]4
Co(II), d7 system, electronic configuration in octahedral is t2g5eg2 and CFSE is -0.8 Δo+2P.
Then calculate CFSE for tetrahedral [CoCl4]2
Electronic configuration in tetrahedral is e4 t23 and CFSE is -1.2 Δt +2P.
Now covert CFSE for tetrahedral geometry to CFSE for octahedral geometry:

Δo = -1.2 Δt  4/9
= -0.533 Δo
OSSE = [-0.8 – (-0.533)] Δo
= -0.2667 Δo
OSSE of -0.2667 Δo is not sufficient to compensate higher coulombic repulsion in octahedral
geometry. Thus tetrahedral geometry is more preferred for Co(II) in presence of weak field
like chloride.
OSSE is a determining factor whether a transition metal spinel would adopt regular
structure or inverse structure.

The spinels are a class of minerals with general formula of AB2X4 which crystallise in the
cubic (isometric) crystal system, with the X anions (typically chalcogens, like oxygen and
sulfur) arranged in a cubic close-packed lattice and the cations A and B occupying some of
the octahedral and tetrahedral sites in the lattice.
General formula is AB2O4 if it is oxide, where oxidation state of A metal ion is +2 and
oxidation state of B metal ion is +3 as in MgAl2O4.
So we can write the formula as AII(BIII)2O4.

A spinel unit cell is made up of 8 face centred cubic (FCC) cells. The anions (usually oxide
ions: O2) occupy the FCC lattice points. Thus in spinel unit cell there is 32 oxide anion
(O2). Actual composition of spinel is then (AII)8(BIII)16O32. These 32 oxide anion produce 32
octahedral sites and 64 tetrahedral sites in the unit cell.
Partial occupancy of both tetrahedral and octahedral sites i.e.1/8th of tetrahedral and ½ of the
octahedral sites are occupied by metal ions.

Normal Spinel
2+ 3+
 Chemical formula: (A )(B )2O4
 Examples are many aluminates such as MgAl2O4, FeAl2O4, CoAl2O4 and a few
ferrites such as ZnFe2O4 and CdFe2O4.
2+ 3+
 In this structure, all the A ions occupy the tetrahedral sites and all the B ions
occupy the octahedral sites.

Inverse Spinel

 Chemical formula: (A2+)(B3+)2O4 but can be more conveniently written as B(AB)O4.

 Most ferrite follow this structure such as Fe3O4 (or FeO.Fe2O3), NiFe2O4, CoFe2O4
etc.
 In this structure, ½ of the B3+ ions occupy the tetrahedral sites and remaining ½
B3+ and all A2+ ions occupy the octahedral sites [thus formula is written as
B(AB)O4]. Simply, we can say A2+ metal ions exchange sites with half of B3+ metal
ions.
Both normal and inverse structures are known for transition metals containing spinel
Let us take example of Fe3O4 (or FeO.Fe2O3) and Mn3O4 (or MnO.Mn2O3)

In Fe3O4 calculate OSSE for both Fe(III) and Fe(II) system (oxide is weak field ligand and
can enforce both octahedral and tetrahedral geometry)

Fe(III), d5 system, electronic configuration in high spin octahedral complex is t2g3eg2 and
CFSE is 0.
Electronic configuration of Fe(III) in tetrahedral complex is e3t22 and CFSE is again 0.
The OSSE value is 0 for Fe(III). Now as there is no OSSE, if half of the Fe(III) ions occupy
tetrahedral sites then overall coulombic repulsion in the system can be lowered which
will stabilize the system.

Let us calculate OSSE for Fe(II)

Fe(II), d6 system, electronic configuration in weak field octahedral complex is t2g4eg2 and
CFSE is -0.4 Δo+ P.
Electronic configuration of Fe(II) in tetrahedral geometry is e3t23 and CFSE is -0.6 Δt + P.
Now covert CFSE for tetrahedral geometry to CFSE for octahedral geometry:

Δo = -0.6 Δt  4/9
= -0.266 Δo
OSSE = [-0.4– (-0.266)] Δo
= -0.134 Δo
Due to this OSSE Fe(II) ions in Fe3O4 will occupy octahedral sites instead of tetrahedral
sites and half of the Fe(III) ions will occupy tetrahedral sites instead of octahedral.

Thus Fe3O4 is inverse spinel.

In Mn3O4 calculate OSSE for both Mn(III) and Mn(II) system

Mn(II), d5 system, thus CFSE 0 for both high-spin octahedral and tetrahedral complex.
No OSSE, Mn(II) ions will occupy tetrahedral sites.

Let us calculate OSSE for Mn(III)

Mn(III), d4 system, electronic configuration in weak field octahedral complex is t2g3eg1 and
CFSE is -0.6 Δo
Electronic configuration of Mn(III) in tetrahedral geometry is e2t22 and CFSE is -0.4 Δt
Now covert CFSE for tetrahedral geometry to CFSE for octahedral geometry:

Δo = -0.4 Δt  4/9
= -0.177 Δo
OSSE = [-0.6– (-0.177)] Δo
= -0.423 Δo
Mn(III) ions will occupy octahedral sites due to favourable OSSE value. So, Mn3O4 is
normal spinel.
Splitting d-orbitals in other fields

Experimental evidences of d-orbital splitting and CFSE

Ionic Radii

The Effect of d-orbital splitting on the radii of the divalent ions of first transition series
(consider octahedral high-spin complexes). Dotted line shown in the graph is the theoretically
predicted trend (predicted based on the effects of screening and variation in effective nuclear
charge (Zeff), assuming a spherical distribution of the 3d electrons.) for the ionic radii and
double humped curve is experimentally obtained. Only three metal ions, Ca2+ (d0), Mn2+
(high-spin d5), and Zn2+ (d10) lie on the theoretical curve. All other divalent ions show lower
ionic radii due to asymmetrical distributions of d electrons. In Sc2+ ion, single d-electron will
occupy t2g orbitals. As the lobes of the t2g orbitals are directed in between the ligands, the d-
electron is unable to shield the ligands from the nuclear charge. Consequently, the ligands
experience a higher effective nuclear charge than predicted, the metal–ligand distance will be
shorter than the expected consequently the ionic radius will be smaller than the expected. If
the d-electron was distributed uniformly over all five d orbitals, they would be much more
effective screening of the ligands from the nuclear charge, making the metal–ligand distances
longer and giving the metal a larger ionic radius. It can be observed from the above curve
whenever d-electrons occupy t2g orbitals ionic-radii decreases and ionic-radii increases with
occupancy of eg orbitals.
Hydration Energies
The hydration energy of a metal ion is defined as the change in enthalpy for the following
reaction:
M2+ (g) +  H2O (l) → [M(H2O)6]2+ (aq)
The plot of the hydration energies of the first-row transition divalent ions versus atomic
number forms a curve with hump. The dashed line is theoretically calculated and only the
three divalent cations with spherically symmetrical distributions of d electrons (Ca2+, Mn2+,
and Zn2+) lie on the dashed lines. The dashed line corresponds to hydration energies
calculated based solely on electrostatic interactions. Subtracting the CFSE values for the
[M(H2O)6]2+ ions from the experimentally determined hydration energies gives the points
shown as open circles, which lie very near the calculated curve. Therefore, CFSEs are
primarily responsible for the differences between the measured and calculated values of
hydration energies.

Effect of d-orbital splitting on of the divalent first transition series metal ions versus atomic
number (solid circles) shows large deviations from the smooth curve calculated, assuming a
spherical distribution of d electrons (dashed line). Correcting for CFSE gives the points
shown as open circles are close to the calculated values.

Lattice Energies

The lattice energy is defined as the negative of the enthalpy change for the reaction below.

M2+ (g) + 2Cl (g) → MCl2 (s)

The shape of the lattice-energy curve is essentially the mirror image of the hydration-energy
curve with only Ca2+, Mn2+, and Zn2+ lying on the smooth curve. The explanation for the
deviations from the curve is exactly the same as for the hydration energy data: all the
transition-metal dichlorides, except MnCl2 and ZnCl2, are more stable than expected due to
CFSE.
A plot of the lattice energies for the first-row transition metal dichlorides versus atomic
number shows similar deviations from the smooth curve calculated, assuming a spherical
distribution of d electrons (dashed lines).

Factors affecting the magnitude of Δ

1. Geometry
The magnitude of crystal field splitting (∆) depends on the geometry. For example ∆o > ∆t or
∆sq > ∆t
2. Oxidation state of the metal cation
The higher the oxidation state of the metal cation, the greater will be the magnitude of ∆. The
higher the oxidation state of the metal facilitates the ligand to approach more closely to it
and, therefore the higher splitting of metal d-orbitals is expected due to greater repulsion
between metal d-electrons and ligand.

∆o for [Fe(H2O)6]2+ < ∆o for [Fe(H2O)6]3+

3. Same oxidation state of metal cations but the number of d-electrons

is different
In general, for a given series of transition elements, in complexes having the metal cation
with the same oxidation state but the different number of electrons in the d-orbitals, the
magnitude of ∆0 decreases with increase in the number of d-electrons. It is due to the fact that
the higher number of d-electrons prevents the ligands to come closer to the metal cation.
∆o for [Co(H2O)6]2+ = 9200 cm-1(3d7)
∆o for [Ni(H2O)6]2+ = 8500 cm-1(3d8)

4. Same number of d-electrons in metal cations but oxidation state is different

In general, for a given series of transition elements, in complexes having same number of d-
electrons but with different oxidation state, the magnitude of ∆o increases with increase of the
oxidation state. As the higher the oxidation state of the metal facilitates the ligand to
approach more closely to it.
K3[CoF6] (3d6, oxidation state is +3, complex is high-spin, paramagnetic system)
whereas K4[NiF6] (3d6, oxidation state is +4, complex is low-spin, diamagnetic system,
magnitude of ∆o increases due to +4 oxidation on nickel and a low-spin complex formed in
presence of weak field fluoride ligand)
5. Principal quantum number (n) of the d-orbital of the metal cation
In case of complexes having the metal cation with the same oxidation states and the same
number of d-electrons, the magnitude of for analogous complexes within a given group
increases about 30% to 50% from 3d to 4d and by about the same amount from 4d to 5d. It is
because:
(a) On moving from 3d to 4d and 4d to 5d, the size of the d-orbital increases and electron
density decreases in them. Moreover with increase of principle quantum number d-orbitals
are more diffused. Therefore the ligands can approach the metal cation with larger d-
orbital more closely. The close approach increases the repulsion interaction.
(b) The steric hindrance is less around a larger metal cation.
∆o for [Co(NH3)6]2+ = 23000 cm-1
∆o for [Rh(NH3)6]2+ = 34100 cm-1
∆o for [Ir(NH3)6]2+ = 41200 cm-1

6. Nature of Ligands

The ligands are classified as a weak and strong ligand. The ligand which causes a small
degree of splitting of d-orbitals are called weak ligands and the ligands which cause a large
splitting are called strong ligands. The common ligands have been arranged in order of their
increasing crystal field splitting power to cause splitting of d-orbitals from a study of their
effects on the spectra of transition metal ions.

(weak end)O22−< I− < Br− < S2− < SCN− (S–bonded) < Cl− < N3− < F−< NCO− <
OH− < C2O42− < H2O < NCS− (N–bonded) < CH3CN < gly (glycine) < py (pyridine) < NH3 <
en (ethylenediamine) < bipy (2,2'-bipyridine) < phen (1,10-phenanthroline) < NO2− < PPh3 <
CN− < CO (strong end)
This order is usually called as Spectrochemical series
The order of the field strength of common ligands is independent of the nature of the metal
cation and the geometry of the complex.
The order of the spectrochemical series can be explained from the nature of the
ligands ie. depending upon their donor or acceptor abilities. Ligands such as H2O or NH3, are
σ bond donors only, with no orbitals of appropriate symmetry for π bonding interactions.
Bonding by these ligands to metals is relatively simple, using only the σ bonds to create
relatively weak interactions. The position of these only σ-donor ligands is as moderately
strong to weak field in the spectrochemical series. Other examples of only σ bonding ligands
are ethylenediamine, py, glycine etc.
The ligands having σ-donation and π-donation character are regarded as weak field
ligand. These ligands have available occupied p orbitals as π donors. These types of ligands
tend to donate these electrons to the metal along with the σ bonding electrons, exhibiting
stronger metal-ligand interactions and an effective decrease of Δ (vide infra). Most halide
ligands as well as O2− and OH− are prime examples of weak field ligands.
When ligands have low-lying vacant π* orbitals and in metal ion filled d orbitals of
suitable energy are available, there is the possibility of pi-backbonding. These ligands act as
σ-donor and π acceptor type ligand and Δ value increases (vide infra). Ligands such as
bipyridine, 1,10-phenanthroline, CN−, CO are the examples of strong field ligand.
The trend of the spectrochemical series can be explained with the help of molecular
orbital theory (MOT). But in MOT we have to consider the covalent nature of the metal-
ligand bonds which contradicts the assumption of CFT (metal-ligand interaction is
electrostatic in nature). This modification of CFT was proposed by van Vleck. His theory is
known as adjusted crystal field theory (ACFT) or more commonly ligand field theory (LFT).
In LFT, overlap between metal orbitals with ligand orbitals is considered.

Why H2O is relatively strong field than O2− or OH−?

H2O is only σ donor ligand whereas O2− or OH− are σ-donor and π-donor type ligands. Effect
of π-donor ability can be explained with the help of partial MO diagram.

The ligands having better π-donation character will act as weak field ligand more. As π-
donation character increases ligand field becomes weaker.

Why CN−, CO behave as strong field ligand? (Next page)

 Colour of Complexes
Electronic transition / absorption spectroscopy

The origin of the variety of colour in transition metal complexes has intensely been
investigated by chemists. For example, aqueous solutions of [Fe(H2O)6]3+ are red,
[Co(H2O)6]2+ are pink, [Ni(H2O)6]2+ are green, [Cu(H2O)6]2+ are blue and [Zn(H2O)6]2+ are
colourless. Interestingly the octahedral [Co(H2O)6]2+ is pink, but the tetrahedral [CoCl4]2- is
blue. The green colour of [Ni(H2O)6]2+ converts to blue when ammonia is added to produce
[Ni(NH3)6]2+. The origin of the colour can be explained from CFT.
Origin of electronic transition

When a sample absorbs all wavelength of visible light (400-800 nm), then the sample appears
to be black as none reaches our eyes from that sample. On the other hand, if the sample
absorbs no visible light, it is white or colourless. When the sample absorbs a particular
photon of visible light, our eyes see the complementary colour eg. if the sample absorbed
orange colour, it would appear blue; blue and orange are said to be complementary colours.

d-d transitions

The colour of transition metal complexes mostly arise from electronic transitions between
one d-orbital to another d orbital and referred as d-d transitions (for examples: t2g and eg for
the octahedral complexes and e and t2 for the tetrahedral complexes). The colours observed
are related to the magnitude of. Since the magnitude depends on factors such as the
geometry of the complex, the nature of the ligands and the oxidation state of the central metal
atom. Thus difference in colours can easily be explained if we can understand the geometry
and splitting.
Besides d-d transitions we can observe colour due to Ligand to Metal Charge Transfer
(LMCT) and Metal to Ligand Charge Transfer (MLCT).
 In the d-d transitions, when  value is large we observe colour at lower wavelength
side, eg. if violet light absorbed yellow colour observed. When  value is small we observe
colour at higher wavelength side, eg. if yellow light absorbed violet colour observed.

Selection rules for electronic transitions

The absorption spectra of coordination complexes govern by two selection rules. The
transition that violates the selection rules is known to be ‘forbidden’ transition.

The Laporte Selection Rule

In a molecule a centre of symmetry (octahedral or square planar), transitions are not allowed
between same orbitals, for example d to d. The Transitions are only allowed when l = ±1,
i.e. the orbital quantum number should differ by 1.
(Δl = lf – li), where Δl is equal to lf (total angular momentum of the final state) subtracted by
li (total angular momentum of the initial state). Thus s→s, p→p, d→d or f→f transitions are
not allowed. The geometries affected by this rule include octahedral and square-planar
complexes. The rule is not applicable to tetrahedral complexes as it does not contain a centre
of symmetry.

Spin Allowed - Spin Forbidden Rule

Any transition for which S  0 is strongly forbidden, that is, in order to be allowed, spin
multiplicity, (2S+1), must same for ground state and excited state.

As d-d transitions are governed by these selection rules, the intensity of the d-d
transitions is low (low molar absorption coefficient). Tetrahedral complexes are normally
bright in colour than octahedral complexes as only spin selection rule is applicable as there is
no centre of symmetry and Laporte rule does not hold well for d-d transition.

Q. [TiCl6]3- exhibits one d-d Transition with a shoulder. Explain.

Ans. Octahedral [TiCl6]3-, d1 system should give only one d-d transition. However, Jahn-
Teller distortion occurs to eliminate the degeneracy of the system. Due to the distortion, t2g
and eg levels split again, consequently a shoulder appeared.