CML 101: Introduction to Chemistry

Crystal field 5 lectures

Theory

Course detail
Inorganic
Chemistry
Organome-
Metals in
3 lectures tallic
Biology 4 lectures
Chemistry

Instructor: Dr. Biswarup Chakraborty

Phone: 011-2659-8481
Email: cbiswarup@chemistry.iitd.ac.in Lecture notes are available as pdf files.
 5 lectures
Introduction to Coordination Chemistry and Crystal Field Theory, Crystal Field
Stabilization Energy, Explaining physical properties, magnetic properties,
distortion of shape and color of complexes using CFT

Crystal field
Theory

Coordination
Chemistry Introduction to organometallic
Role of transition metals such as Fe
chemistry, The 18 electron rule,
and Zn in biological systems, Organome-
Metals in Metal Carbonyls and sandwich
Cytochromes, Myoglobin, tallic
Biology compounds, Unique reactions of
Hemoglobin, and Carbonic Chemistry
organometallics and their use in
anhydrase
explaining homogeneous catalysis
3 lectures
4 lectures
Reference Books

Crystal field
Theory

Coordination
Chemistry
Organome-
Metals in
tallic
Biology
Chemistry
 Introduction to Coordination Chemistry: Historical background
➢ Coordination compounds have been used as pigments and dyes since antiquity.

Egyptian Roman
Coloured Coloured
Statue Statue

First ever synthetically produced color pigment was Egyptian blue also known
as cuprorivaite, prepared around 2,200 B.C.

Prussian blue, KFe[Fe(CN)6] or FeIII[FeIIIFeII(CN)6]3 Royal Blue, [Cu(NH3)4(H2O)2]2+ Aureolin, K3[Co(NO2)6]·6H2O

First prepared by the paint maker Used to paint British Royal First prepared by by Nikolaus
Diesbach in Berlin around 1706. Navy Uniform since 1748. Wolfgang Fischer in 1831
The formulas of these compounds were deduced in the late nineteenth century, providing background for
the development of bonding theories.

Sophus Mads Jørgensen Christian Wilhelm Blomstrand

➢ Blomstrand and Jørgensen’s Chain theory in late nineties
Proposed that the nitrogens could form chains
with those atoms having a valence of 5
For an example,

1826–1894
1837–1914
Hexaamminecobalt(III) chloride, [Co(NH3)6]Cl3

According to this theory, chloride ions attached directly to cobalt were bonded more strongly than
chloride bonded to nitrogen.
Experimental evidence: Reaction of following cobalt salts with AgNO3 and gravimetric analysis of
AgCl (ppt) obtained
[Co(NH3)6]Cl3, [Co(NH3)5]Cl3, [Co(NH3)4]Cl3, [Co(NH3)3]Cl3
Invalidity of Chain Theory and Werner’s theory of Coordination Sphere

1. Number of ions from the cobalt compounds 2. Two different colour of same compound

[Co(NH3)6]Cl3, [Co(NH3)5]Cl3,, Aqueous

AgNO3 AgCl (ppt)
[Co(NH3)4]Cl3 , [Co(NH3)3]Cl3

[Co(NH3)4Cl2]+

Green isomer Violet isomer

[Co(H2NC2H4NH2)2Cl2]+

Number of ions for a complex ion can be explained Two different structures with the same formula for
by Werner’s Theory a complex ion can be explained by Werner’s Theory
 Coordination Compounds: Primary and Secondary Coordination Sphere
Alfred Werner
➢ Werner proposed an octahedral structure for compounds and they are
stabilized by coordination bonds.
Primary coordination sphere: ions/ligands directly attached to central metal ion
Secondary coordination sphere: ions/ligands not directly attached to central metal ion

1866-1919
Nobel Prize in
Chemistry 1913 [Co(NH3)6]Cl3 [Co(NH3)5]Cl3

➢ Isomerism (to explain different colour) ➢ Optically active pure inorganic compound

Werner’s
Carbon-Free Optically
Active Compound,
[Co{Co(NH3)4(OH)2}3]Br6
trans-green cis-violet
 Coordination Chemistry of Twentieth Century
Finding an explanation for the observed properties of transition metal complexes such as color, magnetism, shape of complexes

Variation of some physical properties Magnetic properties of complexes

of metal complexes across a period

Temperature dependence of magnetic moments

Structure and reactivity of metal ion biology Color of metal complexes

 Attempt to describe bonding of coordination compounds
➢ Valence d-orbitals available in d-block metal complexes

The formation of a
dz2 orbital from a
linear combination
of dz2—y2 and dz2—x2
orbitals.

dz2 dx2—y2

dzx dyz dxy

 Bonding in Coordination Compounds: Valence Bond Theory (VBT)
Theories of Bonding in transition metal complexes were proposed (1930 onward) considering the hybridization of available valence orbitals:
Hybrid orbitals may be formed by mixing the characters of atomic orbitals that are close in energy. The character of a hybrid orbital depends
on the atomic orbitals involved and their percentage contributions.

Linus Pauling
Nobel 1954,1962

Hybridization
and geometry
correlation from
VBT
of different
coordination
complexes.
 Limitations of VBT
For octahedral Fe(III) complexes (d5), we must account for the existence of both high- and low-spin complexes.

Low spin iron complex: [Fe(CN)6]3-

High-spin iron complex: [Fe(F)6]3-

The two d orbitals required for the sp3d2 hybridization scheme must come from the 4d set. However, this scheme is unrealistic
because the 4d orbitals are at a significantly higher energy than the 3d atomic orbitals

Nickel(II) (d8) forms paramagnetic tetrahedral and octahedral complexes, and diamagnetic square planar complexes.

It cannot tell us why certain ligands are associated with the formation of high- (or low-)spin complexes.
It can say nothing about origin of color of certain complex, electronic spectroscopic properties or about the kinetic inertness.
Valence bond theory may rationalize stereochemical and magnetic properties, but only at a simplistic level
 Crystal Field Theory: First Proposed in 1929 by Hans Bethe
This is an electrostatic model and simply uses the ligand electrons to create an electric
field around the metal centre. Ligands are considered as point charges and there are no
metal–ligand covalent interactions.

dx2‒y2, dz2
dxy, dxz, dyz
Hans Bethe
ΔO
Δt Nobel Prize, 1967

dx2‒y2, dz2
Tetrahedral crystal field dxy, dxz, dyz Octahedral crystal field

CFT can explain various properties of Transition Metal Complexes:

1. Geometry of the complex
2. Structural distortions
3. Stability and Activity of complexes (inert or labile)
4. Origin of Color (transitions)
5. Magnetism (paramagnetism or diamagnetism)
6. Lattice Energy, Ionic Radii
 Crystal Field Theory: The Octahedral Crystal Field
Basic Assumptions:
Metal ion in an octahedral field
•The ligands and the metal are considered as point
charges Mn+
•The attraction between the metal and the ligands is
purely electrostatic Metal ion in a spherical Field
•Properties of the metal complexes are explained based
on changes happening to the d orbitals of the metal only
3dz2 3dx2—y2
Mn+

Isolated metal ion Degenerate

Energy

3d atomic orbitals 3dxy 3dyz 3dzx

Orbital Mn+
energy The 3d atomic orbitals are split
Into two levels
Degenerate
3d atomic orbitals If the electrostatic field created If the electrostatic filed created by
by point charge ligand is the point charge ligands in
spherical, the energies of the octahedral, 3d orbitals that points
Metal ion Mn+ and six
electrons in the 3d orbitals are directly at the ligands have higher
ligands L at infinite
raised uniformly energy
distance away
Orbitals affected when ligands approach a metal in an octahedral arrangement

d-orbitals having lobes pointing directly at x,y and

z axis are repelled most by electron-electron
repulsion The orientation of the five d orbitals with
respect to the ligands of an octahedral
complex: the degenerate eg and t2g orbitals

➢ A triply degenerate level is labelled t

➢ A doubly degenerate level is labelled e
➢ The subscript g means gerade and the
subscript u means ungerade.
➢ The u and g labels are applicable only
if the system possesses a centre of
d-orbitals not pointing directly at x, y and z axis are symmetry (centre of inversion) and
stabilized to maintain the overall energy same thus are used for the octahedral field
 Ligand Field Strength
➢ The magnitude of ΔO is determined by the strength of the crystal field, the two extremes being called weak field and
strong field
ΔO (weak field) < ΔO (strong field) High Spin Vs. Low Spin (d1 to d10) complex

➢ When does a complex prefer High Spin / low spin arrangement of electrons?
o < Pairing energy : High Spin o > Pairing Energy : Low Spin

o P
[Fe(H2O)6 ]2+ d6 9350 19150 High Spin o < P
[Fe(CN)6 ]4- d6 32200 19150 Low Spin o > P