AKS_Lecture 20

BITS Pilani
Pilani Campus
CHEM F111 : General Chemistry

Lecture 20
Coordination Chemistry Ajay K. Sah
BITS Pilani, Pilani Campus
Discussed topics……
 Crystal field splitting in tetrahedral complex
 Calculation of CFSE for octahedral and tetrahedral complexes
 Uses of CFSE in understanding of:
 stabilization of oxidation state
 lattice energy
 hydration energy
 ionic radii
Crystal Structure of Spinels: Close-packed Structure

Crystal structure of spinels
Explanation of Crystal Structure of Spinels using CFT:
Spinels, AB2O4: A(II); B(III); O2-
Structure: Cubic Close Packed
Structure of Anions and
cations occupy the empty sites
(holes/ voids)
No. of Tetrahedral sites: 2N

(N= no. of anions per unit cell)
No. of Octahedral sites: N
In normal Spinel: (A2+[B3+2]O42-)

A(II) occupy the tetrahedral sites
B(III) occupy the octahedral sites
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Crystal Structure of Spinels:
In Inverse Spinel: (B3+[A2+B3+]O42-)
A(II) occupy the Octahedral sites
B(III) occupy the Octahedral and Tetrahedral sites
Compare the structures of Mn2+Mn23+O4 and Fe2+Fe23+O4
Mn3+ (d4) Mn2+ (d5) Fe3+ (d5) Fe2+ (d6)
CFSE -0.60 Δo 0 0 -0.40 Δo

(Octahedral weak field)
CFSE (Tetrahedral weak field) -0.18 Δo 0 0 -0.27 Δo

Identify the preferred spinel structure for NiFe2O4
Ni is in +2 oxidation state, d8 configuration
In tetrahedral void, configuration: e4t24, CFSE = -0.8 Δt (0.36 ΔO)
In an octahedral void, configuration: t2g6eg2, CFSE = -1.2 ΔO
Fe is in +3 oxidation state, d5 system
In tetrahedral void, Configuration: e2t23, CFSE = 0
In octahedral void, configuration: t2g3eg2, CFSE = 0
Hence, Ni2+ prefer to stay in the octahedral void
Therefore, inverse spinel structure, FeIII[NiIIFeIII]O4
Magnetic property
Weak field Strong field
t2g4eg2 t2g6eg0
eg
eg
E o E o Octahedron
d6
t2g t2g
CFSE = -0.4o CFSE = -2.4o
PARAMAGNETIC DIAMAGNETIC
How do we measure the magnetic property??

Magnetic Moments
Weak field Strong field
t2g4eg2 t2g6eg0
eg
eg
E o E o Octahedron
d6
t2g t2g
CFSE = -0.4o CFSE = -2.4o
PARAMAGNETIC DIAMAGNETIC
m(spin only) = [4(4+2)]½ BM m(spin only) = 0
= 4.89 BM
Thus, given a value of m and the oxidation state of M, we can find the crystal field d-
electronic configuration as well as the CFSE
Tetragonal distortion
Cube with an octahedron inside Tetragonal system

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Distortion of Oh complexes
 If all the six distances between the ligand and central metal ion are the same are
said to be regular (i.e., symmetrical) octahedral complexes
 If the distances are not equal are said to be
distorted octahedral complexes
(a) Diagonally distorted octahedral complexes
- distortion takes place along a two-fold
axis
(b) Trigonally distorted octahedral complexes -
distortion takes place along a three-fold
axis
(c) Tetragonally distorted octahedral
complexes – distortion takes place along a
four fold axis
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Distortion: tetragonal elongation
Tetragonal complexes may be obtained by any of the following two
ways:
(a) If the two trans ligands lying on the z-axis in an octahedron are
moved away from the central metal cation so that their distance
from the metal cation is slightly greater than it is for the other four
ligands lying in the xy plane, we get a tetragonal structure.
Two long bonds
elongated
Distortion: tetragonal compression
(b) If the two trans ligands located at the z-axis are brought near the
central metal cation so that their distance from the metal cation is
smaller than it is for the other four ligands in the xy plane, we again
get a tetragonal structure.
Two short bonds
compressed

Tetragonal distortion
Natural distortion due to different kinds of bondings: No Jahn-Teller Distortion
Example: [MnF2Cl4]4- Example: [MnF4Cl2]4-
Elongation
along z-axis
Compression
along z-axis
Jahn-Teller theorem
In 1937, Jahn-Teller theorem explain why certain six-coordinated
complexes undergo distortion to assume distorted octahedral (i.e.,
tetragonal) geometry.
This theorem states that “any non-linear molecular system possessing
degenerate electronic state will be unstable and will undergo
distortion to form a system of lower symmetry and lower energy and
thus will remove degeneracy”.
NB: Jahn-Teller theorem only predicts the occurrence of a distortion;
it does not predict its nature or its magnitude.

Jahn-Teller distortion

Symmetrical electronic arrangements
Electronic t2g eg Nature of Examples
configuration ligand field
d0 Strong or weak TiO2, [TiF6]2-

d3 Strong or weak [Cr(oxalate)3]3-,
[Cr(H2O)6]3+
d5 Weak [MnF6]4-, [FeF6]3-
d6 Strong [Fe(CN)6]4-, [Co(NH3)6]3+
d8 Weak [NiF6]4-, [Ni(H2O)6]2+
d10 Strong or weak [Zn(NH3)6]2+, [Zn(H2O)6]2+

Asymmetrical electronic arrangements
Electronic t2g eg Nature of ligand Examples
configuration field
d1 HS or LS
d2 HS or LS
d4 Strong field (LS)
d4 Weak field (HS) Cr(II) and Mn(III)
d7 Strong field (LS) Co(II) and Ni(III)
d9 Either strong or Cu(II)
weak
Condition for distortion
No distortion condition: t2g and eg sets as symmetrical orbitals
Condition for slight distortion: When d-orbitals of the central metal

ion of an octahedral complex have t2g orbitals as unsymmetrical
orbitals, there occurs slight distortion in the complex
Condition for strong distortion: When the eg orbitals which point

directly towards the ligands, are unsymmetrical i.e., contain 1, 3, or
2(only in LS complex) electrons, strong distortion

Symmetrically filled orbitals
E
eg eg
t2g t2g
Z-elongation Δo >> δ1 > δ2 Δo >> δ1 > δ2 Z-compression


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BITS Pilani

CHEM F111 : General Chemistry

BITS Pilani, Pilani Campus

No. of Tetrahedral sites: 2N

In normal Spinel: (A2+[B3+2]O42-)

CFSE -0.60 Δo 0 0 -0.40 Δo

BITS Pilani, Pilani Campus

CFSE = -0.4o CFSE = -2.4o

How do we measure the magnetic property??

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CFSE = -0.4o CFSE = -2.4o

Cube with an octahedron inside Tetragonal system

Two long bonds

Two short bonds

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Example: [MnF2Cl4]4- Example: [MnF4Cl2]4-

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d0 Strong or weak TiO2, [TiF6]2-

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Condition for slight distortion: When d-orbitals of the central metal

Condition for strong distortion: When the eg orbitals which point

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Z-elongation Δo >> δ1 > δ2 Δo >> δ1 > δ2 Z-compression

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