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-
Different Bonds
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
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
Fig. A
Fig. B
BONDING THEORIES IN
COORDINATION COMPLEXES
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
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
1s
1s
2s
2p
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
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+
O
O
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
3d
4s
4p
[Co(NH3)6]3+
3d
4s
4p
4d
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
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
[Mn(H2O)6]3+
(octahedral)
4p
4d
SP3d2
3d
4s
[Mn(NO2)6]3(octahedral)
4p
d2SP3
4d
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.
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.
or sp3d2
Those in which the charge of the lone pair of electrons for donation is focused in only one direction.
(CFT) is used to provide explanation for the spectra and magnetic properties of
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
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
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
For d1-d3 systems: The electrons will not pair; will occupy the t2g set (Hund's rule)
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
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
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.
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.
TETRAHEDRAL FIELD
none of the metals d-orbitals point exactly in the direction of the ligands
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)
Octahedron
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
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.
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.
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
MCl2(s)
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
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.
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.
recall MO
diagram for
CO.
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
Summary of the MO
splitting in an Oh
geometry with respect
to the ligand type
Mn2+ < Ni2+ < Co2+ < Mo2+ < Re4+ < Fe3+< Ir3+ < Co3+ < Mn4+