CHAPTER-COORDINATION COMPOUNDS

MODULE-4 –CRYSTAL FIELD THEORY

Students will be able to:

• Draw the crystal field splitting in an octahedral and tetrahedral field
• List the factors determining the magnitude of the crystal field splitting
energy,∆
• Write the electronic configuration on central metal ion in terms of t2g and eg.
• Understand the reason for Colour of complexes.(d-d transition)
• List the limitation of of crystal field theory
• Understand synergic bonding in metal carbonyl
• State the factors affecting Stability of complex

CRYSTAL FIELD THEORY

https://www.youtube.com/watch?v=xTTgUcumYv0

• This theory is based on the assumption that the metal ion and the ligands act as
point charges and the interaction between them is purely electrostatic i.e, metal –
ligand bonds are 100 % ionic

• The five d orbitals in an isolated gaseous metal atom are degenerate. When a
ligand approach the central metal atom, the degeneracy of d orbital is lost and d
orbitals split into two groups which have different energies. This is called
crystal field splitting.

• The energy difference between the two sets of the d-orbitals in the crystal
field is known as the crystal field splitting energy, ∆.

CRYSTAL FIELD SPLITTING IN AN OCTAHEDRAL FIELD

• Here the six ligands approach the metal atom exactly along the X, Y and Z axis.

• Hence dx2-y2 and dz2 orbitals which lie on the axes experience greater repulsion
than dxy, dyz, dxz which lie in between the axis .
• Hence the energies of dx2-y2 and dz2 is raised and the energies of dxy, dyz, and
dxz is lowered.

• For complexes in a ligand field, d orbital occupancy depends on ∆o and pairing

energy, P.

• If ∆o > P, - electron pair up in lower energy d orbitals first and forms low spin
complex. Ligands for which ∆o > P are called strong field ligands.

• If ∆o< P, electrons spread out among all d orbitals before they pair up and
forms high spin complex. Ligands for which ∆o < P are called weak field
ligands.

Strong Field Ligand------- Large ∆o------------------------------low spin complex

Weak field ligand----------- Small ∆o-------------------high spin complex

CRYSTAL FIELD SPLITTING IN A TETRAHEDRAL FIELD

• Here the four ligands approach the metal atom not along the X, Y and Z axis, but
in between the axis.

• Hence dx2-y2 and dz2 orbitals which lie on the axes experience less repulsion than
dxy, dyz, dxz which lie in between the axis.

• The energies of . dx2-y2 and dz2 is lowered and the energies of dxy, dyz, and dxz
is raised.
• Here the d orbital splitting is inverted and smaller as compared to octahedral
field splitting.

• The value of crystal field splitting energy for tetrahedral coordination entity is
4/9 times the value for octahedral field.

Factors determining the magnitude of the crystal field splitting energy, ∆

• Oxidation state of the metal ion- Higher the charge on the central metal ion, the
greater the value of ∆.

• Geometry of the coordination entity – The ∆ value for tetrahedral coordination

entity is 4/9 times the value for octahedral field.

• Nature of ligand–Ligands which affect only a small degree of crystal field

splitting are termed as weak ligands and those which affect a large splitting are
called strong field ligands. The ligands can be arranged in the increasing field
strength in Spectrochemical series. In this series, the ligands are arranged in
the increasing order of the magnitude of crystal field splitting.

I-< Br- < SCN- < Cl-< S2-< F- < OH- < C2O42- < H2O < NCS- < edta-< NH3 < en <
NO2- < CN- < CO
Colour of complexes.
https://www.youtube.com/watch?v=_06Of_0x1wI

• The electron present in the d subshell absorbs light of particular wavelength

from the visible region and gets excited to higher level within the same d
subshell and the colour we see is the complementary colour of what is been
absorbed. This is called d-d transition.
• The amount of d-orbital splitting depends on the strength of ligands, thus
different ligands have different splitting energies and different colors result.

• Large ∆o = higher energy light absorbed (shorter wavelengths).

• Smaller ∆o = lower energy light absorbed (longer wavelengths).

Let us consider three complexes of Co+3 as [Co(H2O)6]3+, [Co(NH3)6]3+ and
[Co(CN)6]3- . According to Spectrochemical series, the CFSE will be in the order,
H2O < NH3 < CN-

[Co(H2O)6]3+ [Co(NH3)6]3+ [Co(CN)6]3-

∆o value Small Intermediate Large

Excitation Energy Small Intermediate Large

Absorption Wavelength Large Intermediate Small

Colour Absorbed Orange Blue Violet

Colour Transmitted Blue Yellow Orange Yellow

Limitation of crystal field theory

• It does not take into consideration the covalent character of bonding between
ligand and the central atom.

• Ligands are considered as point charges and is expected that anionic ligands
should exert the greatest splitting effect , which is not actually found so.
METAL CARBONYL
https://www.youtube.com/watch?v=BmTszkMsRyg&t=52s
• These are organometallic compounds which contain one or more metal-carbon
bonds.
• Metal carbonyl are homoleptic complexes containing carbonyl ligands only
Eg: Ni(CO)4 Fe(CO)5 etc.

Structures of metal carbonyl

Bonding in metal carbonyls;

Here the metal carbon bond has both sigma and Π character due to back bonding.
Because of this synergic effect, bonding in metal carbonyl is strong.
• Overlap of filled orbital of CO with suitable empty metal orbital resulting in the
formation of sigma bond between metal and ligand.(M<-----C)
• Π – overlap involving filled metal d- orbital and empty antibonding π orbital of
CO.(Back bonding) ( M ----→C)

Stability of complexes
• The stability of a complex depends on the degree of association between the
metal and the ligands involved in the state of equilibrium.

Factors affecting stability

• Greater the charge on the metal ion, greater is the stability of the complex ion.
• If the ligand has more than one donor atom and forms a chelate, it increases the
stability of the complex.

Application of coordination compounds

https://www.youtube.com/watch?v=4T7trTDasOQ

In Biological systems –
• The pigments responsible for photosynthesis is coordination compound of
magnesium.
• Hemoglobin is coordination compound of iron.
• Vitamin B12 is a coordination compound of Cobalt.

In Analytical Chemistry
• It is used in many qualitative and quantitative chemical analysis.
• Hardness of water is estimated by titration with EDTA.
In medicinal chemistry
• EDTA is used in lead poisoning
• cis-platin is used to inhibit the growth of tumors.

In extraction/metallurgy of metals
• Extraction process of Au and Ag make use of complex formation.
• Purification of Ni can be achieved through formation, followed by decomposition
of their coordination compounds.

.
SOLVED QUESTIONS :

Q1. With the help of Crystal Field Theory, predict the number of electrons in [Fe
(CN)6]4- and [Fe ( H2O )6]2+ complexes .
Ans: In both the complexes, Fe is present as Fe (II). It has d6 configuration, i.e , 4
unpaired electrons are present. As CN- is a strong ligand, these electrons will
pair up. Hence, unpaired electrons = 0. But H2O is a weak ligand, electrons
will not pair up. Hence unpaired electrons = 4.

Q2. [NiCl4]2- is para magnetic while [Ni (CO)4 ]is diamagnetic, though both are
tetrahedral. Why?
Ans: In [ NiCl4 ]2-, Ni is in +2 oxidation state with the configuration of 3d8 4s0. Cl- is
a weak ligand. It cannot pair up the electrons in 3d orbitals. Hence, it is
paramagnetic.
In [Ni (CO)4], Ni is in zero oxidation state with the configuration 3d8 4s2. In the
presence of CO ligand, the 4s electrons shift to 3d to pair up 3d electrons.
Thus, there is no unpaired electron present. Hence, it is diamagnetic.

Q3. [Fe(H2O)6]3+ is strongly paramagnetic [Fe(CN)6]3- is weakly paramagnetic.

Explain.
Ans: In both the complexes, Fe is in +3 oxidation state with the configuration 3d 5.
CN- is a strong ligand. In it’s presence, 3d electrons pair up leaving only 1
unpaired electron. The hybridization is d2sp3 forming inner orbital complex.
 H2O is a weak ligand. In it’s presence, 3d electrons do not pair up. The
hybridization is sp3d2 forming an outer orbital complex containing 5 unpaired
electron. Hence it is strongly paramagnetic

Q4. On the basis of crystal field theory, write the electronic configuration for d4
ion if ∆o > P in an octahedral field.
Ans: In this case, the 4th electron will enter into t2g, i.e., pairing will take place in one
of the t2g orbitals. Hence, the configuration will be t2g4.

Q5. What happens to the colour of the coordination compound when the ion
[Ti(H2O)6]3+ is heated gradually?
Ans: On heating its color disappears. This is because the ligand water which is
responsible for crystal field splitting and color, is lost.

Q6. Why are low spin tetrahedral complexes not formed?

Ans: This is because for tetrahedral complexes, CFSE is lower than pairing energy.

Q7. Give the electronic configuration of d orbitals in the following Complex on

the basis of Crystal Field Splitting Theory.
[CoF6]3-, [Fe(CN)6]4- [CoF4]2-
Ans: [CoF6]3- = t2g4 eg2

[Fe(CN)6]4- = t2g6 eg0

[CoF4]2- =( eg)4 t2g 3

Q8. Arrange the following complex ions in increasing order of crystal field
splitting energy (∆o).
[Cr(Cl)6]3- , [Cr(CN)6]3- , [Cr(NH3)6]3+
Ans: From the spectrochemical series, CFSE of the ligands is in the order: Cl- < NH3
< CN-.
Therefore [Cr(Cl)6]3- < [Cr(NH3)6]3+ <[Cr(CN)6]3-

Q9. Why do complexes having similar geometry have different magnetic

moment?
Ans: The difference is due to presence of weak and strong ligands. If ligand is
strong (high CFSE), electrons will not pair up. Hence magnetic moment will
be high. E.g. [CoF6]3- and [Co(NH3)6]3+ both are octahedral but former is
paramagnetic while latter is diamagnetic.

Q10. Among octahedral and tetrahedral crystal fields, in which case the
magnitude of crystal field splitting is larger?
Ans: It is larger in case of octahedral crystal field ( ∆t = 4/9 times of ∆o).

Q11. Why is the bonding in metal carbonyl strong?

Ans: Here the metal carbon bond has both sigma and Π character due to back
bonding .Because of this synergic effect, bonding in metal carbonyl is strong.
Q12. Among [Fe(ox)3 ]3- and [FeF6]3- ,which is more stable and why?
Ans: [Fe(ox)3 ]3- is more stable because oxalate is a bidendate ligand structures
which can form chelates .

ASSIGNMENT:

1. Define Crystal Field Splitting Energy. On the basis of Crystal Field Theory,
write the electronic configuration of d4 ion if ∆o < P., in a tetrahedral field.

2. Draw a sketch to show the splitting of d-orbitals in an octahedral crystal field.

State for a d6 configuration, how the actual configuration of the d-orbitals in
an octahedral crystal field is decided by the relative values of ∆o and P.

3. The Hexaaquamanganese (II) ion contains 5 unpaired electrons while the

Hexacyano ion contains only one unpaired electron. Explain using Crystal
Field Theory.

4. On the basis of crystal field theory explain why Co (III) forms paramagnetic
octahedral complex with weak field ligands whereas it forms diamagnetic
octahedral complex with strong field ligands.

5. CuSO4. 5H2O is blue in color while CuSO4 is colorless. Why?

6. Compare the magnetic behavior of the complex entities [Fe (CN)6]4- and
[FeF6]3. (Fe = 26)

7. How does crystal field theory explain?

i) High spin and low spin states of complexes.
ii) Magnetic property of complexes
iii) Color of complexes

8. What is the basis of formation of spectrochemical series?

9.Do we call metal carbonyls as organometallics? Why or why not?

10.What is the relation between overall stability constant and stepwise stability
constant?
11. NCERT Exercise : 9.15, 9.16, 9.17, 9.18, 9.19, 9.20, 9.21.

For Your Reference :

https://www.youtube.com/watch?v=xTTgUcumYv0
https://www.youtube.com/watch?v=_06Of_0x1wI
https://www.youtube.com/watch?v=BmTszkMsRyg&t=52s
https://www.youtube.com/watch?v=4T7trTDasOQ