ISOMERISM IN COORDINATION COMPOUNDS

Definition: Isomerism is a phenomenon in which two or more compounds have the same molecular
formula but different structural or spatial arrangements. The compounds are called isomers.
Different arrangement of atoms due to their different structures are responsible for their
different physical or chemical properties.
Coordination compounds show two main types of isomerism-

(a) Structural Isomerism

Different Bonds

Different Chemical Formulas

Different Name

(b) stereo Isomerism

Same Bonds, Different Orientations
Same Chemical Formulas
Different Name

Ionisation isomerism: Occurs when there is an exchange of two anionic groups within and outside
the coordination sphere. i.e when the counter ion in a complex salt acts as a ligand and the ligand of
the complex becomes counter ion. In order words there is a mutual exchange between counter ion
and ligand. The two forms of the complex are called ionisation isomers.
[Co(NH3)5Br]SO4 (violet) and [Co(NH3)5SO4]Br (red)
Coordination Isomerism: Coordination Isomerism: Occurs when the ligands are interchangeable
between cationic and anionic entities of different metal ions present in the complex. i.e there is a
redistribution of ligands between two metal centres in a complex
[Co(NH3)6][Cr(CN)6] and [Cr(NH3)6][Co(CN)6]
Linkage Isomerism: Occurs in the coordination compounds containing ambidentate ligands which can
coordinate to the metal through at least two different binding sites. So two types of structures are
formed which are called linkage isomers.
E.g
[Co(NH3)5(NO2)]Cl2 : NO2 can bond to the metal either with N or with O
Nitro-N
In yellow complexes

Nitrito-N
In red complexes

Hydrate Isomerism: Occurs when solvent molecules e.g water is

either directly bound to the metal ion (ligand) or may be present as
free solvent molecules in the crystal lattice as water of
crystallisation. There are many isomers which differ in the position of
water molecules in their formula. For example, there are three known
hydrate isomers of CrCl3(H2O)6:
[Cr(H2O)6]Cl3 (violet)
[Cr(H2O)5Cl]Cl2.H2O (pale green)
[Cr(H2O)4Cl2]Cl.2H2O (dark green)

Stereo Isomerism
Stereoisomerism occurs in complexes due to difference in spatial arrangement of ligands round the
central metal. i.e they arise due to stereochemical deposition of their ligands. They are further
classified as follows:
(i) Geometrical isomerism: This type of isomerism arises in heteroleptic coordination complexes due to
different possible geometric arrangements of the ligands. The most common type of geometrical
isomerism involves cis and trans isomers in square planar and octahedral complexes.
Example: Platinum ammine complexes [Pt(NH3)Cl2]:
Coordination number 4

Coordination number 6

OPTICAL ISOMERISM
(a) Optical isomers are mirror images of each other and have chiral
centers.
(b) Optical isomers exist in complexes that are not superimposable on
their mirror images and they do not have a plane of symmetry.
(c) Optical isomers have similar physical and chemical properties but
differ in their ability to rotate the plane of polarized light: They
rotate the plane of polarised light in opposite direction
(d) Isomer which rotates the plane polarized light to the right is
called dextro rotatory (d-form) and the isomer which rotates the
plane polarized light to the left is called laevorotatory (lform)

(e) A mixture of optical isomers of the same quantity will not rotate
the plane of polarized light because the effect of one isomer is
cancelled out by the other. Such a mixture is called racemic mixture

 optical isomers or enantiomers are mirror images

of each other.
Just as a right hand will not fit into a left glove,
two enantiomers cannot be superimposed on each
other.

 Most of the physical properties of chiral

molecules are the same, boiling point,
freezing point, density, etc.
One exception is the interaction of a chiral
molecule with plane-polarized light.

 If one enantiomer of a chiral compound is placed

in a polarimeter and polarized light is shone
through it, the plane of polarization of the light
will rotate.

If one enantiomer rotates the light 32 to the

right, the other will rotate it 32 to the left.

Fig. A

Fig. B

Note that compounds in Fig A are

superimposable but compounds in Fig B are
not superimposable. But all the compounds
have the same molecular formular!!

BONDING THEORIES IN
COORDINATION COMPLEXES

Simply put, chemical bonds are the

attractive forces that hold atoms
together to form compounds.

Metal complexes are formed by the

donation of lone pairs of electrons into
the empty d-orbitals of the metal ion

Different Bonding theories

Effective Atomic Number Rule (EAN) Rule
Valence Bond Theory (VBT)

Crystal Field Theory (CFT)

Adjusted Crystal Field Theory (ACFT) (LFT)
Molecular Orbital Theory (MOT)

EAN Rule
The EAN rule states that stable compound should have electronic
configuration of its nearest noble gas
Based on the fact that noble gasses are chemically inert, and
compounds tend towards the most stable configuration.
Explains the bonding in metal complexes with metal in zero
oxidation state e.g [Ni(CO)4] and [Cr(CO)6],
Limitation: The variation in coordination number of metal ions
could not be explained by this theory.
Hence the need for another theory

VBT

..introduced to explain the reason for the variation

in coordination number based on the number of
hybridized orbitals of the metal used in bonding

How does valence-bond approach

explain the formation of chemical
bonds?

Overlap of Atomic Orbitals

Valence bond method considers the SHARING OF ELECTRONS between atoms

(to form a covalent bond) as a result of overlap of atomic orbitals of the
bonding atoms. Electrons stay in regions between the two atoms.

Valence bond theory limitations:

It cannot explain relative stability of complexes
It cannot explain the concept of colours and magnetic properties of complexes

Because of orbital overlap, the bonding

electrons localize in the region between the
bonding nuclei such that
There is a high probability of finding the
electrons in the region between the bonding
nuclei.

VBT continues..

Lets move away from complexes and take a simple case of a diatomic molecule and see how atomic orbitals
overlap to form a hybrid orbitals: H2, HF

Overlap of two half-filled orbitals leads to

the formation of a covalent bond.
1s

1s

1s

1s-1s overlap gives a H H single bond

2s

2p

The 1s-2p overlap gives a H F single bond

VBT continues..

Non-bonding electrons: these are the electrons that do not participate in the bonding business
They are found in some molecules and exert some repulsive forces on other electron

2s

2p

2s

2p

Non-bonding electrons

Each F atom has three pairs of non-bonding electrons.

VBT continues..
Overlap of an empty orbital with a fully-filled
orbital leads to the formation of a co-ordinate
covalent bond or dative bond
H
H

H+

Represented by an arrow pointing from the

electron pair donor to the electron pair acceptor.

O
O

..Now lets come back to

VALENCE BOND THEORY IN METAL COMPLEXES

Describes bonding in coordination complexes by

considering the hybridization of the orbitals involved in
the bonding and stereochemical consequences of the
hybridization.

Account for the stereochemistry, kinetic

behavior of complexes, and magnetical
properties of many complexes

Complexes are formed by the use of 3d

orbitals as inner complexes and those formed
by the use of 4d orbitals as outer complexes.

The inner orbital complexes have less

number of unpaired electrons: low spin
complexes.

The outer orbital complexes have

more number of unpaired electrons: high
spin complexes.

According to VBT, bonding occurs through the following mechanism:

i.

Dissociation of the salt to make the cation (M+) available for coordination.

ii.
Hybridization of atomic orbitals of the cation required to accommodate
the electron pairs to be donated
iii.
Rearrangement of electrons in the atomic orbitals of the cation, where
necessary to ensure that the hybridized orbitals are free to accommodate the
donated electron pairs.
iv.
Bond formation between the cation and the ligands by overlapping of
atomic orbitals of the ligands containing the lone pair and the hybridized orbitals
of the cation.
v.
Spatial orientation of the ligands to minimize repulsion between them
leading to stereochemistry (shape) of the complex.

Understanding hybridization
Hybridization occurs when atomic orbitals mix together to form new orbitals.
The new orbitals formed have the same total electron capacity as the old ones;
and both the properties and the energies of the new, hybridized orbitals are an
'average' of the original un-hybridized orbitals

E.g in CH4, C = 1s2 2s2 2p2

for carbon to form a
bond with hydrogen,
four hybrid orbitals
are required since
there are four atoms
attached to the
central carbon atom

the three 2p orbitals of the C atom are

combined with its 2s orbital to form four new
orbitals called "sp3" hybrid orbitals

Examples in metal complexes

Consider these common complexes in the next slides; pay attention on the hybridization of
the metal orbitals, and their subsequent filling with the electrons from the ligand orbital.
The blue arrow indicate the spin of electrons from the metal ion, while the red denotes the
spins of the electron from the ligands
[Co(NH3)6]3+

3d

4s

4p

[Co(NH3)6]3+

3d

4s

4p

4d

Note the electronic configuration of the transition- metal ion

The valence-shell orbitals, 4s and 4p orbitals are empty.

after overlapping with the valence-shell orbitals of the ligands, new hybrid orbitals are formed.

In 4-coordinate complexes
Generally, tetrahedral complexes are high spin complexes while square planar complexes are low spin complexes.
(a) Tetrahedral

3d8

Cl-

3d

4s

Cl-

Cl-

Cl-

[Ni(Cl)4]2(Tetrahedral)
4p
SP3

4d

(b) Square planer complexes

3d8

CN-

CN-

CN- CN-

[Ni(CN)4]2(Square planer)
3d

4s

4p

4d

dSP2

In 5-coordinate complexes
3d 8

CN -

CN-

CN- CN-

3-

[Ni(CN) 5]

(Square - based
pyramid )
3d

4s

4p
dSP

4d

In 6-coordinate complexes
Octahedral complexes
The concept of the inner and outer d-orbital
3d4

H20

3d

4s

H2O H2O H2O H2O H2O

[Mn(H2O)6]3+
(octahedral)
4p

4d
SP3d2

3d4 NO2- NO2-

NO2- NO2- NO2- NO2-

3d

4s

[Mn(NO2)6]3(octahedral)
4p
d2SP3

4d

OUTER ORBITAL COMPLEXES

The weak field ligands provide less energy to the to the central metal ion and are, therefore,
unable to pair the unpaired electrons in the valency shell of the central metal ion and mostly result
in paramagnetic and outer orbital complexes as outer d-orbitals are used in hybridization.

INNER ORBITAL COMPLEXES

The strong field ligands provide enough energy to the central metal ion which is greater than the
pairing energy of the electrons. Hence unpaired electrons in the valency shell of the metal ion get
paired making available inner d orbitals of lower energy for hybridization resulting in diamagnetic
inner orbital complexes

Note that:

The number of unpaired electrons determines the magnitude of the magnetic properties of
the complexes.

Complexes without paired electron are diamagnetic while those with unpaired electrons are
paramagnetic in nature.

In [Ni(CN)4]2-, the two unpaired electron in the Ni2+ d orbitals are forced to pair up due to
the approach of strong CN- ligand unlike Cl- which has less repulsion effect on the unpaired
electrons in [Ni(Cl)4]2- complex.

Tutorial: [CoF6]3- is paramagnetic while [Co(NH3)6]3+ is diamagnetic. Using VBT,

explain the difference in their magnetic properties

or sp3d2

There are two types of ligands:

(i)

strong field ligands

Those in which the charge of the lone pair of electrons for donation is focused in only one direction.

(ii) weak field ligands

Those in which the charge of the lone pair of electrons for donation is diffused in more than one
direction.

Crystal Field Theory (CFT)

..Addresses the limitation of the VBT

(CFT) is used to provide explanation for the spectra and magnetic properties of
complexes.

LIMITATIONS: It cannot explain the reason for some

degree of covalence in some complexes

CFT
CFT is a purely electrostatic model, and assumes electrostatic interaction between positively
charged metal centre and negatively charged anions or polar molecules

It derives its name from the electrostatic force (field) which is produced when a metal ion is
surrounded by anions in a crystal.
The field generated changes the energies of the d orbitals of the metal center.

CFT approach considers the metal as positive point charge and the ligands as negative point
charges
The positive charge on the metal is the source of attraction on the ligands

The ligands are also repelled by the d-orbital electrons of the metal.
The repulsion on the d-orbital electrons is not uniform leading to splitting of the d-orbitals.
The splitting of the orbitals results in loss of degeneracy among the 5 d-orbitals.
The pattern of splitting is dependent on the coordination number and stereochemistry of the

OCTAHEDRAL FIELD
.STUDY the shapes and orientations of the d orbitals
of transition metal.
In a free gaseous metal ion, the 5 orbitals are
degenerate (of equal energy).
The 5 orbitals remain degenerate in a spherical
electrostatic field with a higher energy since all will
be equally raised by the same amount
The two orbitals of the eg, are raised by 3/5o or 6Dq
while the t2g orbitals are lowered by 2/5o or 4dq
relative to barycentre

The energy separation between the lower energy level t2g and the upper energy
level eg is referred to as crystal field splitting energy, and is denoted by o

-LIGAND ION SERIES

o is dependent on:
Nature of the ligands-the smaller the size of the anions the greater the splitting.

Ligands which cause a small splitting are Weak field ligands (CFSE in the range 7000 - 30000 cm-1) and those
that cause large splitting are Strong field ligands (CFSE typically > 30000 cm-1)
In complexes of same metal ion and the same coordination number, the degree of splitting is dependant on the
nature of the ligand.

Thus, it is possible to arrange ligands according to their ligand field splitting capacity. The series of
ligands arranged this way is called as the spectrochemical series of the ligands.
CO ~ CN- > NO2- > en > NH3> py > NCS- > H2O ~ ox > OH- > F- > Cl- > SCN- > Br- > I
Strong field
Weak field

METAL ION SERIES

The charge on the metal ion-the higher the oxidation state or the primary valence of the
metal the greater the splitting.
The type of d-orbital involved in the bonding scheme- the splitting pattern in 5d is the
greatest because it spread more into space than others.
Just as we have for ligands, it is also possible to arrange metal ions in terms of the
splitting of the d orbitals produced by a given ligand and stereochemistry.
The arrangement which is independent on the nature of the metal is called spectrochemical
series of the metal ions.
For first-row metal ions the arrangement is:
Mn3+> Co3+ > V3+ > Cr3+ > Fe3+ > V2+ > Fe2+ > Co2+ > Ni2+ > Mn2+
From the series, it can be observed that the higher the oxidation state the greater the
splitting

Illustration of o
[Ti(H2O)6]3+ : a d1 complex and the e occupies the lowest energy orbital, i.e. one of the three
degenerate t2g orbitals.

The purple colour is a result of the absorption of light which results in the promotion of this
t2g electron into the eg level.
t2g1eg0 > t2g0eg1

Case when there are more than 1 electron in d orbitals

In this case, the electron-electron interactions must be taken into account.

For d1-d3 systems: The electrons will not pair; will occupy the t2g set (Hund's rule)

For d4-d7 systems: two possibilities arises

(i) The electrons are paired in the t2g set; a low spin case or strong field
situation.
(ii) The electrons are not paired but put in the eg set, which lies higher in
energy; high spin case or weak field situation.

Energy Level diagram

To draw an Energy level diagram, the following steps are followed:

1)
Determine the oxidation state of the metal ion in the complex
2)
Calculate the corresponding number of d electrons
3)
Establish how these electrons occupy the energy level diagram (each energy level can hold max
of 2 electrons)
Pairing Energy, P: This is the energy required to force two electrons into the same orbital
Remember that from d1 to d3, electrons occupy the t2g levels
P becomes important when dealing with d4 -d7 situations upward. Two options arise:
1) If o < P, the 4th electron occupies the eg level, with a spin parallel to those of the t2g electrons.
This is known as the weak-field or high-spin case-t2g3eg1.
2) If o P, the 4th electron occupies the t2g level, where it has to be spin paired. This is known as the
strong-field or low-spin case-t2g4eg0.
Therefore, there are two important parameters to consider:
The Pairing energy (P), and the eg - t2g Splitting (also known as 0, 10Dq or CFSE)

Crystal field stabilization energy

The crystal field stabilization energy (CFSE) is the decrease in energy in going from a spherical situation to an
octahedral crystal field OR
the stability that results from placing a transition metal ion in the crystal field generated by a set of ligands

It is calculated as the energy of the electron configuration in the ligand field minus the energy of the
electronic configuration in the isotropic field.
i.e

CFSE=E= Eligand fieldEisotropic field

E.g the CFSE for V2+ in an Oh site:

V2+ has a d3 electron and they will all go to the t2g orbitals. Hence CFSE for V2+ is (3 X 2/5)o = 6/5 o
This calculation is simple because there is no pairing of electron. When there is pairing of electrons,
then pairing energy P is considered also

CFSE for a d7 Oh complex

High Spin
The splitting pattern and electron configuration
for both isotropic and octahedral ligand fields
are shown below.

CFSE for a d7 Oh complex

Low Spin
The splitting pattern and electron configuration for
both isotropic and octahedral ligand fields are shown
below.

The energy of the isotropic field:

Eisotropic field = 7 0 + 2P = 2P
The energy of the octahedral ligand field:
Eligand field = (52/5o) + (23/5o) + 2P
= 4/5o + 2P

The energy of the isotropic field:

Eisotropic field = 7 0 + 2P = 2P
The energy of the octahedral ligand field:
Eligand field = (62/5o) + (13/5o) + 3P
= 9/5o + 3P

Thus, CFSE = Eligand field Eisotropic field

= (4/5o + 2P) 2P = 4/5o

Thus, CFSE = Eligand field Eisotropic field =

(9/5o + 3P) 2P = 9/5o + P)

Crystal Field Stabilization Energies (CFSE) for high and low spin octahedral complexes
Total delectrons

Isotropic Field

E
0

isotropic field

Octahedral Complex

High Spin
configuration

E
ligand field

Crystal Field
Stabilization Energy

Low Spin
configuration

High Spin

Low Spin

ligand field

d
1
d

0
0

t2g eg
1
0
t2g eg

0 o
-2/5 o

t2g eg
1
0
t2g eg

0 o
-2/5 o

0 o
-2/5 o

0 o
-2/5 o

t2g eg

-4/5 o

t2g eg

-4/5 o

-4/5 o

-4/5 o

t2g eg

-6/5 o

t2g eg

-6/5 o

-6/5 o

-6/5 o

t2g eg

-3/5 o

t2g eg

-8/5 o + P

-3/5 o

-8/5 o + P

t2g eg

0 o

t2g eg

-10/5 o + 2P

0 o

-10/5 o +
2P

t2g eg

-2/5 o + P

t2g eg

-12/5 o + 3P

-2/5 o

-12/5 o +
P

2P

t2g eg

t2g eg

-9/5 o + 3P

-4/5 o

-9/5 o + P

3P

t2g eg

-6/5 o + 3P

-6/5 o

-6/5 o

4P

t2g eg

-3/5 o + 4P

-3/5 o

-3/5 o

10

5P

t2g eg

-4/5 o +
2P
-6/5 o +
3P
-3/5 o +
4P
0 o + 5P

0 o + 5P

t2g eg
t2g eg

t2g eg

High-Spin Versus Low-Spin Octahedral Complexes

Octahedral transition-metal ions with d1,

d2, or d3 configurations

Octahedral transition-metal ions with d4,

d5, d6 or d7 configurations

Octahedral transition-metal ions with d8,

d9, or d10 configurations

JAHN TELLER DISTORTIONS

Jahn Teller theory states that any non linear molecular system in a degenerate
electronic state will be unstable and will undergo some sort of geometrical
distortion to lower its symmetry and remove the degeneracy.
Distortion is inevitable if there is unsymmetrical occupation of
degenerate orbitals.

Metal ions with d9 (Cu2+) and d4 (Cr2+) high spin in octahedral field
usually have distorted octahedral shapes due to unequal number of
electrons occupying the eg orbitals.

JAHN TELLER DISTORTIONS continues

Consider a d9:

the two orbitals of eg cannot contain the same number of electrons, there will be
two electrons in one orbital and one electron in the other.

The orbital with two e- will have greater repulsion for ligands on its axis
compared to the orbital with one e-.

Thus, all the ligand-metal bond length will not be equal hence distortion occurs in
the complex.

Consequences of Jahn Teller distortion

.Compression and expansion of bond lengths

(i) If the orbital with the greater number of electron is dz2:

the ligands along the z-axis will not be as close to the metal centre
as others.
The ligands in dz2 direction will have longer ligand-metal bond
length.
This will result in elongation distortion along the Z-axis.

(ii) If the dx2-y2 contains greater number of electrons compared to

dz2 in an octahedral field:

the ligands along the x and y plane will experience greater

repulsion
This will lead to increase in length of the ligands along the
equatorial region, the octahedron will be compressed along the z
axis.

TETRAHEDRAL FIELD
none of the metals d-orbitals point exactly in the direction of the ligands

here four ligands form a tetrahedron around the metal ion

the d-orbitals are in between the ligands in the crystal field.

the triply degenerate orbitals (dxy, dyz and dxz) are closer to the ligands path on approaching the metal
centre than the doubly generate orbitals (dx2-y2 and dz2)
consequence: (dxy, dyz and dxz) are higher in energy than (dx2-y2 and dz2)

The magnitude of the splitting in a tetrahedral field is designated as t.

t 0 ; Reasons: 1) four ligands produce the field in Td as against sixligands in Oh complex
2) none of the d orbitals in Td point directly at the ligands in the tetrahedral field
For identical ligands in a complex and related metal-to-ligand distances, t = (4/9)o.

When to Expect Tetrahedral Geometry

When the ligands are large. This is mainly to avoid 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.)

Sketch the d-orbital energy levels and distribution of d-electrons in the following complexes
1.
2.
3.
4.
5.

Zn(Cl)42- (tetrahedral)
Ti(H2O)62+(octahedral)
NiCl42- (tetrahedral)
CoF63- (high-spin complex)
Co(NH3)63+ (low spin complex)

SQUARE PLANAR COMPLEX

This arrangement can be obtained from octahedral model by removal of the two ligands pointing directly along
the z axis.
Consequence: 1) decrease in repulsion experienced along the z-axis
2) orbitals with z component will experience decrease in energy and greater stability.
3) The energy of dz2, dxz and dyz will be reduced while those of dx2-y2 and dxy will increase.

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 Clleads to the formation o f a square planar complex, for example, [PdCl4]2- .

Octahedron

square planer geometry

o Square planar geometry can also be achieved by the removal of a pair of ligands from the z-axis of
an octahedron, leaving four ligands in the x-y plane.
o For transition metal compounds, the crystal field splitting diagram for square planar geometry can thus be
derived from the octahedral diagram.
o The removal of the two ligands stabilizes the dz2 level, leaving the dx2-y2 level as the most destabilized.
o Consequently the dx2-y2 remains unoccupied in complexes of metals with the d8configuration

FACTORS AFFECTING CRYSTAL FIELD SPLITING

i.

The nature of the ligands- the smaller the size of the anions the greater the splitting.
This can be observed with the halides F- > Cl- > Br- > I-. Similarly, ligands with ability
to
form -bond cause greater splitting. Co > CN- > phen > NO2-.
ii. The higher the oxidation state or the primary valence of the metal the greater the
splitting. Generally, M3+ ions cause greater splitting than M2+ ions.
iii. The type of d-orbital involved in the bonding scheme, the splitting pattern in 5d is
the greatest because it spread more into space than others.
LIMITATION OF CRYSTAL FIELD THEORY (CFT)
Although crystal field theory provides insight to spectra and magnetic properties of complexes
through the concept of strong and weak field ligands, it still has the following limitations:
1) it cannot account for the position of the ligands in the spectrochemical series and

1) it cannot also explain the reason why some degree of covalency is observed in a number of
complexes.

Applications of crystal field theory

Magnetic Properties: CFTthrough the splitting of the d-orbital in the electrostatic strong or weak
field env. has aided the prediction of the magnetic prop. of complexes.
Diamagnetism: found in elements with paired electrons. Complexes without unpaired electrons are
diamagnetic in nature.
- it is a characteristic of d0 and d10 complexes, and also other d-config. with no unpaired e-s.
Paramagnetism: occurs in complexes of transition metals containing ions with partially filled d
orbitals and all substances with unpaired electrons; e.g. free atoms, free radicals.
Electronic absorption spectra: An important characteristic of the transition metal ions and their
complexes is their colour.
The origin of the colour is attributed to the partial filling of the d-orbitals, which makes them
capable of absorbing light energy in the visible region.
The absorbed photon causes electronic transitions between different energy levels within split dorbitals.
In an electronic transition, an electron is excited from an occupied to an empty orbital. The
difference in energy corresponds to the energy of the photon.
Orgel diagram for d3 config., and Tanabe-Sugano diagram for the d8 config.

Consequences and applications of crystal field theory

The energy level splitting of the d-orbitals as a consequence of their interaction with the ligands in a complex
has important structural and thermodynamic effects on the chemistry of transition-metal complexes
Structural Effects: (1) ionic radii
consider the ionic radii of the divalent fourth-period metal ions versus atomic number shown below

The dashed line represents the behavior

predicted based on the effects of screening and
variation in effective nuclear charge (Zeff),
assuming a spherical distribution of the 3d
electrons.
Only Ca2+(d0), Mn2+ (high-spin d5), and Zn2+ (d10) lie
on the smooth dashed curve.
All other divalent ions fall below this curve
because they have asymmetrical distributions of d
electrons

When the e-s are in the t2g orbitals e.g in Ti2+, because they are directed
between the ligands, the two d-electrons are unable to shield the ligands from
the nuclear charge. Consequently, the ligands experience a higher effective
nuclear charge than predicted, the metalligand distance is unusually short, and
the ionic radius is smaller than expected.

(2)The JahnTeller Effect

JahnTeller distortions are most important for d9 and d4 (high-spin) complexes
In Cu2+ complexes, the observed distortion is always
an elongation along the z axis.
In Cr2+ complexes, the observed distortion is mostly
compression along the z axis.
In both cases, however, the net effect is the same:
the distorted system is more stable than the
undistorted system

The increase in the axial metalligand distances in

an octahedral d9 complex is an example of a Jahn
Teller distortion.
J-T distortion causes the degenerate pair of eg
orbitals to split in energy by an amount 1;
1 and 2 are much smaller than o, as a result, the
distorted system is lower in energy than the
undistorted complex by 1/2. Thus more stable

 Thermodynamic Effects
(1) Hydration energy
The hydration energy of a metal ion is defined as the change in enthalpy for the following reaction:
M2+(g)+H2O(l) M2+(aq)
From the figure below, Ca2+(d0), Mn2+ (high-spin d5), and Zn2+ (d10) lie on the smooth dashed curve
because their CFSE is 0. Other metal ions deviate from the expected line due to extra CFSE

(2) 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 hydrationenergy curve with only Ca2+, Mn2+, and Zn2+ lying on
the smooth curve.
All the transition-metal dichlorides, except MnCl2
and ZnCl2, are more stable than expected due to
CFSE.

ADJUSTED CRYSTAL FIELD THEORY (LIGAND FIELD THEORY)

The bond existing in complexes is not purely/completely electrostatic as assumed by CFT.

Electron spin resonance spectra have shown that certain percentage of the electrons is
diffused into the ligand orbital.
CFT is therefore modified to take into account the existence of some degree of
covalence in transition complexes.
The modification of CFT results into Adjusted CFT also called Ligand Field theory (LFT).

If the degree of diffusion or overlap is in excess, the LFT will not hold rather a pure
covalent treatment will be suitable hence the use of Molecular Orbital theory (MOT).

The LFT can be considered as a mid-point between electrostatic and covalent description of
bonding in metal complexes

MOLECULAR ORBITAL THEORY

MOT is a bonding theory which is based on the result of overlap of bonding atomic orbital of the ligands and
the hybridized orbital of the metal leading to formation of both bonding and antibonding molecular orbitals.
It is the most complete theory taking into consideration all possibilities from the electrostatic to
covalent extremes
The fundamental assumption of MOT is that metal and ligand orbitals will overlap and combine provided
they are of the correct symmetry.

In a molecular bonding scheme, the numbers of bonding and antibonding orbitals are equal but the
antibonding orbitals cancelled out the resultant effect of the bonding orbitals.

HOW TO GO ABOUT TRYING TO BUILD A MOLECULAR

ORBITAL DIAGRAM FOR A COORDINATION COMPLEX
Assume the central metal atom has s, p, d orbitals in valence shell = 9 orbitals
Assume each ligand atom, L, has s and p orbitals, 4 X n ligands = 4n orbitals
Thus for Oh, ML6: metal = 9 orbitals
Ligands = 4 X 6 = 24 orbitals
A total number of orbitals in the basis set is 33
Usually 33 orbitals is not practical because orbitals can be grouped according to
special rules dictated by the shape of the molecules:
-bonding- only s, and pz orbitals are engaged
S + Pz
SP
-bonding- only Px, and py orbitals are engage

symmetry adapted linear combinations SALC

Since metals usually have d electrons that are much
higher in energy than those on typical donor atoms
(like o, s, n or p), thus the anti-bonding combinations
will be much closer in energy to the original d orbitals,
because both are relatively high in energy.
The bonding combination will be much closer in energy
to the original ligand orbitals, because these ones are
all relatively low in energy

Building of molecular orbital energy level diagram: CASE 1: -donor only(H-, NH3)
Lets consider an Oh (ie ML6) e.g the complex [Co(NH3)6]3+
Co3+ is a first row metal, and so the valence shell atomic orbitals are 3d, 4s and 4p.
In octahedral symmetry:
The s orbital has a1g symmetry
The p orbitals are degenerate with t1u symmetry, and

sigma-bonding only
molecular orbital
diagram

The d orbitals split into two sets with eg (dz2 and dx2-y2) and
t2g (dxy, dyz and dxz) symmetries.
Each ligand, NH3, provides one orbital.
Thus, six orbitals from the ligands are assigned a1g, t1u and eg symmetries.
The 9 valence metal orbitals are grouped into bonding and nonbonding orbitals
The bonding orbitals are: 4s, 3px, 3py, 3pz, dx2-y2 and dz2 (they lie in the direction of the approaching ligand hence
suitable for overlapping).
The t2g set (dxy, dxz, dyz) which are not exactly in the direction of the approaching ligands are considered non-bonding

The six ligand orbitals and six orbitals of the metal are grouped into six bonding molecular orbitals and six antibonding
molecular orbitals, while t2g orbitals are left as nonbonding molecular orbitals.
Electrons from the ligands are filled into the bonding orbitals while the d electrons are filled into nonbonding t2g orbitals
and Lowest unoccupied Molecular Orbital (LUMO) which are the antibonding orbitals representing the eg set of the metal
d orbitals.

 ACCEPTORS AND DONORS IN MOLECULAR ORBITAL THEORY

The most basic approach considers sigma bonding only (like the diagram in the previous slide), since all ligands
can act as sigma donors. However, in addition to acting as sigma donors, some ligands can act as donors and
acceptors.
In MOT, there are 3 types of ligands viz:

acceptors: CO, NO+, CNR, CN

donors: halides (X-= Cl, Br, I), NH2-(amide), NR2- , O2-, OR-, SR donors: H-, NH3
A ligand with empty * orbitals (eg CO, CN-, NO-) can accept electron density from a metal d-orbital.
This type of bonding is referred to as -back-bonding, and a ligand that undergoes -back-bonding is referred
to as a acceptor
.

recall MO
diagram for
CO.

CASE 2: -acceptor (CO, NO+, CNR, CN)

ML6: M = 9 orbitals: a1g, t1u, t2g, eg
L = 6 orbitals (a1g, t1u, eg)
6 X 2 (Px, Py) = 12 orbitals (t1g, t2g, t1u, t2u)

i.e the group orbitals for interactions have

symmetries of t1g, t2g, t1u, and t2u.
Here, the t2g * of the ligand orbital can interact
with the t2g of the metal orbitals to give new
bonding and anti-bonding molecular orbitals, which
were nonbonding orbitals in the sigma-bonding only
molecular orbital diagram.
Because the t2g set is lowered relative to its
position when -bonding only is considered, o is
thus increased.
The new molecular orbitals formed from the metal d
orbitals and the ligand * orbitals are shown in red

I- < Br- < SCN- < Cl- < F- OH- , ONO- < OH2 < NCS- < NCCH3 < NH3, py < NO2- < CN-, NO, CO
small
large
weak-field ligands
strong-field ligands
-donor ligands
-acceptor ligands
high-spin complexes
low-spin complexes

CASE 3: -donor (halides)

ML6: M = 9 orbitals: a1g, t1u, t2g, eg
L = 6 orbitals (a1g, t1u, eg)
6 X 2 (Px, Py) = 12 orbitals (t1g, t2g, t1u, t2u)

i.e the group orbitals for interactions have

symmetries of t1g, t2g, t1u, and t2u.
A ligand with filled orbitals acts as a donor.
Again, here the ligand t2g orbitals interact with the
metal t2g orbitals, to form bonding and antibonding
orbitals.
But, in this case, because the t2g molecular orbital is
filled with electrons from the ligand, o arises from
the difference between the t2g* and eg* orbitals
Because the t2g set is increased relative to its
position when -bonding only is considered, o is
thus decreased.

Summary of the MO
splitting in an Oh
geometry with respect
to the ligand type

THE NEPHELAUXETIC EFFECT

It is the expansion of the electron cloud of the d-orbital in a metal ion in a complex than they are in the free
ion due to the binding of ligands.
When ligands bind to a metal ion, the orbitals on the metal ion are spread out over a larger region of space
and extend to the orbitals of the ligand.
In molecular orbital terminology, the d-orbital electrons of the metal ion are delocalized
The consequence of nephelauxetic effect is that less energy is required to pair up electrons in the metal ion
than it is for the free ion.
When ligands such as CN-, CO and NO2- are present, the nephelauxetic effect is quite large due to the ability
of the ligands to bond to the metal as a result of back donation.
For complexes with a common metal ion, nephelauxetic effect of ligands varies according to a series
independent of metal ion:
F- < H2O < NH3 < en < ox2- < NCS- < Cl- < CN- < Br- < I
A nephelauxetic series for metal ions independent of ligands is:

Mn2+ < Ni2+ < Co2+ < Mo2+ < Re4+ < Fe3+< Ir3+ < Co3+ < Mn4+