Chemistry

BTCH-101-18

CHAPTER -1
Crystal Field Theory in Octahedral Complexes
NOTES
CFT was given by Hans Bethe in 1929 and was further developed by Van Vlech in 1932. It
explained the bonding in complex compounds.

1. Postulates of CFT:

1. The bonding between metal and ligand is purely electrostatic between metal ion and donor
atom.
2. The central Metal cation is surrounded by ligand which contains one or more lone
pair of electrons.

3. The ionic ligand (F-, Cl- etc.) is regarded as point of negative charges and neutral
molecules (H2O, NH3 etc.) as point dipoles.
4. The electrons of ligand does not enter metal orbital. Thus there is no orbital overlap takes
place.
5. The magnetic properties depend upon the splitting of d- orbitals of the central cation in
different crystal.
6. The color of complexes are explained in terms of electronic transitions between the various
d- orbitals of different energies.
7. It also explains why certain geometries are more favored than others by certain metals in
terms of crystal field stabilization energies.

2. Crystal Field Splitting in Octahedral Complex

• In the case of an octahedral coordination
compound having six ligands surrounding the
metal atom/ion, we observe repulsion between
the electrons in d orbitals of metal and ligand electrons.
• This repulsion is experienced more in the case of dx2-y2 and dz2 orbitals as they point
towards the axes along the direction of the ligand.
• Hence, they have higher energy than average energy in the spherical crystal field.
• On the other hand, dxy, dyz, and dxz orbitals experience lower repulsions as they are
directed between the axes.
• Hence, these three orbitals have less energy than the average energy in the spherical
crystal field.
Thus, the repulsions in octahedral coordination compound yield two energy levels:
• t2g– set of three orbitals (dxy, dyz and dxz) with lower energy.
• eg – set of two orbitals (dx2-y2 and dz2) with higher energy.
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Fig: Splitting of five degenerate d- orbitals into two sets

The energy gap is referred to as D (10 Dq) , the crystal field splitting energy.
eg - higher energy set of orbitals (dz2, dx2-y2)
t2g - lower energy set of orbitals (dxy, dyz and dxz)
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Δo or 10 Dq - The energy separation between the two levels

The eg orbitals are repelled by an amount of 0.6 Δo
The t2g orbitals to be stabilized to the extent of 0.4 Δo.

2.1. Crystal Field Stabilization Energy

In a chemical environment, the energy levels generally split as directed by the symmetry of
the local field surrounding the metal ion. The energy difference between the eg and t2g levels
is given as or 10Dq. It states that each electron that goes into the lower t2g level stabilizes the
system by an amount of -4Dq and the electron that goes into eg level destabilizes the system
by +6Dq. That is the t2g is lowered by 4Dq and the eg level is raised by +6Dq.
For example, the net change in energy for d5 and d10 systems will be zero as shown below.
d5 :- 3(-4Dq) + 2(+6Dq) = -12Dq + 12Dq = 0
d10 :- 6(-4Dq) + 4(+6Dq) = -24Dq + 24Dq = 0
The decrease in energy caused by the splitting of the energy levels is called the “Ligand
Field Stabilization Energy (LFSE)”.

Crystal Field Stabilization Energy Table

The crystal field stabilization energies for some octahedral and tetrahedral complexes of 3d
metal ions are tabulated below.

Electronic Octahedral Complex

Configuration Weak Field (- Strong Field (-Dq)
Dq)
d0 0 0
d1 4 4
d2 8 8
d3 12 12
d4 6 16
d5 0 20
d6 4 24
d7 8 18
d8 12 12
d9 6 4
d10 0 0
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Thus, the crystal field splitting depends on the field produced by the ligand and the charge on
the metal ion. An experimentally determined series based on the absorption of light
by coordination compound with different ligands known as spectrochemical series has been
proposed.
Spectrochemical series arranges ligands in order of their field strength as:
I– < Br– < Cl– < SCN– < F– < OH– < C2O42- < H2O < NCS– < EDTA4- < NH3 < en < CN–<
CO
Filling of d-orbitals takes place in the following manner; the first three electrons are arranged
in t2g level as per the Hund’s rule. The fourth electron can either enter into t2g level giving a
configuration of t2g4eg0 or can enter the eg orbital giving a configuration of t2g3eg1. This
depends on two parameters magnitude of crystal field splitting, Δo and pairing energy, P. The
possibilities of two cases can better be explained as:

• Δo > P – Electron enters in the t2g level giving a configuration of t2g4eg0. Ligands
producing this configuration are known as strong field ligands and form low spin
complexes.
• Δo < P – Electron enters in the eg level giving a configuration of t2g3eg1. Ligands
producing this configuration are known as weak field ligands and form high spin
complexes.

3. Factors Affecting on CFSE of octahedral complexes

1)Nature of metal ion:
e.g. [Co(H2O)6]3+ [Co(H2O)6]2+
Co3+ Co2+
Do=18,200 cm-1 > Do=9,300 cm-1

2)Nature of ligand
a) When the ligands are strong the energy gap between t2g and eg is more the distribution of
electron does not takes place according to Hund’s rule.
These are Low spin Complexes.
b) When ligands are weak CFSE is relatively small hence five d- orbitals are suppose to be
degenerate and therefore distribution of electrons takes place according to Hund’s rule. These
are High spin Complexes.
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Weak field
Ligands (red, high spin)

Strong field Ligands

(violet, low spin)

Electronic Structures of Metal Complexes:

4. Applications of CFT to Octahedral complexes

1) Colour of complexes : The transition metal complexes whose central metal ion contain
partially filled d – orbitals are usually coloured in their solid and solution form.

2) Magnetic Properties :
a) in d1, d2, d3, d8, d9 complexes have same spin state and all are paramagnetic.
b) The low spin d6 and d10 complexes are diamagnetic.
c) In d4, d5, d6 and d7 the number of unpaired electron are different in high spin and
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low spin octahedral complexes .

Thus, Crystal Field Theory provides a basis for explaining many features of transition-metal
complexes. Examples include why transition metal complexes are highly colored, and why
some are paramagnetic while others are diamagnetic. The spectrochemical series for ligands
explains nicely the origin of color and magnetism for these compounds. There is evidence to
suggest that the metal-ligand bond has covalent character which explains why these
complexes are very stable. Molecular Orbital Theory can also be used to describe the bonding
scheme in these complexes.
Crystal Field Splitting in an Octahedral Field

eg

Energy
3/5 o

2/5 o t2g

eg - The higher energy set of orbitals (dz2 and dx2-y2)

t2g - The lower energy set of orbitals (dxy, dyz and dxz)
Δo or 10 Dq - The energy separation between the two levels
The eg orbitals are repelled by an amount of 0.6 0 6 Δo
The t2g orbitals to be stabilized to the extent of 0.4 Δo.
 Tetrahedral Field

t2

2/5 t

Energy
t

3/5 t
e

The higher energy set of orbitals (dxz, dyz, dxy) is labeled

as t2 and the lower energy
gy set ((dz2 and dx2-y2) is labeled
as e.

The crystal field splitting in the tetrahedral field is intrinsically smaller than in the octahedral
field For most purposes the relationship may be represented as Δt = 4/9 Δo
field.
 Octahedral Vs Tetrahedral

Energyy
 [Ti(H2O)6]3+ – a d1 system

The single electron in the t2g orbitals absorb energy in the form of light and gets excited to the eg
orbitals. In case of [Ti(H2O)6]3+, this corresponds to 520 nm (20,300 cm-1).

520 nm
(243 kJ/mol)
 Factors Affecting the Magnitude of Δ
1. Higher oxidation states of the metal atom correspond to larger Δ.
Δ =10,200 cm-1 for [CoII(NH3)6]2+ and 22,870 cm-1 for [CoIII(NH3)6]3+
Δ =32,200 cm-1 for [FeII(CN)6]4- and 35,000 cm-1 for [FeIII(CN)6]3-

2. In groups, heavier analogues have larger Δ.

For hexaammine complexes [MIII(NH3)6]3+:
Δ= 22 870 cm-11 (Co)
22,870 (C )
34,100 cm-1 (Rh)
41,200 cm-1 (Ir)

3. Geometry of the metal coordination unit affects Δ greatly.

Tetrahedral complexes ML4 have smaller Δ than octahedral ones ML6:
Δ= 10,200 cm-1 for [CoII(NH3)6]2+
5,900 cm-1 for [CoII(NH3)4]2+

4. Nature of the ligands.

] Δ in cm-1: 13,100
For [CoIIIL6], 13 100 (F-); 20
20,760
760 (H2O); 22
22,870
870 (NH3)
For [CrIIIL6], Δ in cm-1: 15,060 (F-); 17,400 (H2O); 26,600 (CN-)
 Spectrochemical Series

An arrangement of ligands according to their ability to increase Δ for a given metal center

Weak – I-, Br-, SCN-, Cl-, N3-, F-, H2NC(O)NH2, OH-, ox2-, O2-, H2O, NCS-, py, NH3, en , bpy,
phen, NO2-, CH3-, C6H5-, CN-, CO – Strong

Weak
Strong
Field
Field (Ligand)
 Distribution of Electrons in an Octahedral Complex

Strong field Weak field Strong field Weak field Strong field Weak field

d1 d2 d3

Net energy decrease is called crystal field stabilization energy (CFSE)

For d1, CFSE = 1 × 0.4 = 0.4 Δo

For d2, CFSE = 2 × 0.4 = 0.8 Δo
For d3, CFSE = 3 × 0.4 = 1.2 Δo
 Distribution of Electrons in an Octahedral Complex

There are two possibilities for metal ions having d4-d7

d4 electronic configuration. Depending on the nature of the
ligands and the metal they could be high-spin or low-
2 u.e. spin
i complexes.
l

For the d4 system, CFSE =

4 u.e. For high-spin,
g p ((3 × 0.4)) – ((1 × 0.6)) = 0.6 Δo and
for low-spin, 4 × 0.4 = 1.6 Δo

2.0 Δo 0.0 Δo 2.4 Δo 0.4 Δo 1.8 Δo 0.8 Δo

d5 d6 d7

1 u.e. 5 u.e. 0 u.e. 4 u.e. 1 u.e. 3 u.e.

 Distribution of Electrons in an Octahedral Complex

d8 d9 d10

2 u.e. 2 u.e. 1 u.e. 1 u.e. 0 u.e. 0 u.e.

For d8, CFSE = (6 × 0.4) – (2 × 0.6) = 1.2 Δo

For d9, CFSE = (6 × 0.4) – (3 × 0.6) = 0.6 Δo
For d10, CFSE = (6 × 0.4) – (4 × 0.6) = 0.0 Δo
In all electronic configurations involving two electrons in the same orbital, the actual CFSE is
reduced by the energy spent on pairing the electrons.

Metal ions with 4 – 7 electrons in the d orbital can exist as high-spin

high spin or low-spin
low spin
complexes. Weaker ligands tend to give high-spin complexes, whereas stronger ligands
tend to give low-spin complexes.
Distribution of Electrons in an Octahedral Complex

High-spin Low-spin
d1 t2g1eg0 0.4 Δo t2g1eg0 0.4 Δo
d2 t2g2eg0 0.8 Δo t2g2eg0 0.8 Δo
d3 t2g3eg0 1.2 Δo t2g3eg0 1.2 Δo
d4 t2g3eg1 0.6 Δo t2g4eg0 1.6 Δo
d5 t2g3eg2 0.0 Δo t2g5eg0 2.0 Δo
d6 t2g4eg2 0.4 Δo t2g6eg0 2.4 Δo
d7 t2g5eg2 0.8 Δo t2g6eg1 1.8 Δo
d8 t2g6eg2 1.2 Δo t2g6eg2 1.2 Δo
d9 t2g6eg3 0.6
0 6 Δo t2g6eg3 0.6
0 6 Δo
d10 t2g6eg4 0.0 Δo t2g6eg4 0.0 Δo
 Distribution of Electrons in a Tetrahedral Complex
Tetrahedral
T t h d l splitting
litti is
i seldom
ld large
l enoughh to
t result
lt in
i pairing
i i off the
th electrons.
l t
As a result, low-spin tetrahedral complexes are not common.
A rare example is Cr[N(SiMe3)2]3[NO]

d1 e1 t20 0.6 Δt
d2 e2 t20 1.2 Δt
d3 e2 t21 0.8 Δt
d4 e2 t22 0.4 Δt
d5 e2 t23 0 0 Δt
0.0
d6 e3 t23 0.6 Δt
d7 e4 t23 1.2 Δt
d8 e4 t24 0.8 Δt
d9 e4 t25 0.4 Δt
d10 e4 t26 0.0 Δt
 When to Expect Tetrahedral Geometry

If ligands are large; so as to avoid ligand

ligand-ligand
ligand repulsion

In case of metal ions with zero CFSE (d0, d5 and d10) or

MnO4- ((d0)), FeCl4- ((d5, h.s.),
) ZnCl42- ((d10)

In case of metal ions with small CFSE (d2 and d7)

CoCl42- (d7, h.s.) – 0.8 Δo vs 1.2 Δt
 Square Planar Field

Ligands along the Z

axis are removed from
an octahedral complex
to get a square planar
complex
Energy
 When to Expect Square Planar Geometry

In the case of d8 metals and strong ligands:

Ni2+, in the presence of strong field ligands such as CN- forms a square planar complex.

2nd and 3rd row d8 metals form square planar geometry irrespective of the nature of the
ligand:
With Pd2+ (which already generates a strong field) even a weak field ligand such as Cl-
l d to
leads t the
th formation
f ti off a square planar
l complex,
l for l [PdCl4]2-
f example, 2.