Determine the correct order of splitting energy

[Co ( H2O)6]2+ [Co(H2O)6]3+

[ Ni(H2O)6]2+ [ Ni(NH3)6]2+ [Ni(NO2)6]4-

[ Ni(Cl)6]4- [ Pd(Cl)6]4- [Pt(Cl)6]4-

[ Ni(Cl)4]2- [ Ni(Cl)6]4-
Stability of complex a
Charge of CMI
Stability of complex a
Synergic bonding

Stability of complex a
ligand strength
Stability of complex a
No. of chelate rings
Stability of complex a
Zeff of CMI
EXAMPLE
Determine the correct order of stability :-

(1) [Fe(CN)6]3- [Fe(C2O4)3]3-

(2) [Fe(H2O)6]3+ [ Fe(en)3]3+ [Fe(dien)2]3+

It can be shown that in a tetrahedral structure, none of the d-orbitals
points exactly towards the ligands.
When ligands approaches they are more close to dxy, dyz, dxz in
comparison of dx2 –y2 and dz2 because dxy, dyz, dzx are between the axis

and dz2 and dx2 –y2 are along the axis. So dxy, dyz, dzx feels more repulsion

as compare to dz2 and dx2 –y2 .

Thus, the d orbitals are also split into two groups but in a reverse order
of octahedral complex. The three orbitals, dxy, dyz and dxz, designated
are now have higher energy than the two orbitals .
z

y
x
t2

Energy
0.4 Δt

Barry centre
Δt = crystal field
𝐝𝐱𝐝𝟐−𝐲𝟐 𝐝𝐝
𝐳𝟐𝐲𝐳 𝐱𝐳 𝐝 𝐱 −𝐲𝟐
𝐝𝐝𝐱𝐲 𝟐
𝐝𝐲𝐳 𝐝𝐳𝐱𝐳
𝟐
Splitting energy
of tetrahedral
𝐱𝐲

-0.6 Δt
In presence of ligand
field, energy of d-
orbitals is increased

e
𝐝𝐱𝟐−𝐲𝟐 𝐝𝐳𝟐 𝐝𝐱𝐲 𝐝𝐲𝐳 𝐝𝐱𝐳

In absence of ligand field d-orbitals of metal

01 Complex compounds are mainly coloured due to d-d transition.

Mn+ L

eg

(In d0 & d10 e¯ configuration d-d

transition is not possible)

𝐝𝐱𝟐−𝐲𝟐 𝐝𝐳𝟐 𝐝𝐱𝐲 𝐝𝐲𝐳 𝐝𝐱𝐳

↿ t2g
Colour of complex compounds depends on absorbed energy
02
(Ea) and absorbed wavelength(la).

1 In case of SFL Ea (↑) la (↓)

Eabsorbed 
(Ea)
𝜆𝑎𝑏𝑠𝑜𝑟𝑏𝑒𝑑 (𝜆𝑎 ሻ In case of WFL Ea (↓) la (↑)

Example
[Ni(H2O)6]2+ [Ni(NH3)6]2+ [Ni(NO2)6]4–

Strength of ligand (↑) Ea (↑) la(↓)

For example complementary colour of green is purple
EXAMPLE
Correct increasing order for the wavelengths of absorption in the
visible region the complexes of Co3+ is :

(1) [Co(H2O)6]3+ , [Co(en)3]3+ , [Co(NH3)6]3+

(2) [Co(H O) ]3+ , [Co(NH ) ]3+ , [Co(en) ]3+

2 6 3 6 3

(3) [Co(NH3)6]3+ , [Co(en)3]3+ , [Co(H2O)6]3+

(4) [Co(en)3]3+ , [Co(NH3)6]3+ , [Co(H2O)6]3+

The presence of a ligand is required for the d-d transition

Example

D
TiCl3 TiCl3.6H2O TiCl3
Colourless [Ti(H2O)6]Cl3 Colourless
Violet

CuSO4 D
CuSO4.5H2O CuSO4
Colourless [Cu(H2O)4]SO4.H2O Colourless
Light Blue
Charge Transfer Spectrum

Some compounds of d-block metal shows color due to charge

transfer from cation to anion.

Example

i) KMnO4 Dark violet ii) K2Cr2O7 Orange

iii) Na2CrO4 Yellow iv) CrO2Cl2 Reddish orange
Example

i) KMnO4 Dark violet ii) K2Cr2O7 Orange

iii) Na2CrO4 Yellow iv) CrO2Cl2 Reddish orange

O
O O O

K+ Mn+7 Cr+6 Cr+6

–O O O O
–O
O O–
2K+
Potassium permanganate Potassium dichromate
ISOMERISM

Structural isomerism Stereo isomerism

Ionisation isomerism Geometrical isomerism

Linkage isomerism Optical isomerism

Hydrate isomerism

Coordination isomerism
STRUCTURAL ISOMERISM

Same chemical formula but structure is different .

Types of structural isomerism :-

Ionisation isomerism

Compounds having same chemical formula but give the test of different
type of ions in aqueous solution are known as ionization isomers.
Example

AgNO3
[Co(NH3)5 SO4]Br AgBr (↓) (Yellow ppt.)
Ionisation
isomers
BaCl2
[Co(NH3)5Br] SO4 BaSO4 (↓) (White ppt.)
Hydrate or solvate isomerism

Special type of ionisation isomerism in which no. of water molecules or

polar molecules differ in coordination sphere or outside region.

Example
Chemical formula of complex → CoCl3.6H2O

[Co(H2O)6]Cl3

[Co(H2O)5Cl]Cl2 . H2O

[Co(H2O)4Cl2]Cl . 2H2O are hydrate isomers

CoCl3.6H2O

H2O H2O
H2O H2O H2O H2O
Co Cl3 Co Cl23 . Cl
H2O H2 O H2O H2 O
H2O H2O
Pentaaquachloridocobalt
Hexaaquacobalt (III) chloride
(III) chloride monohydrate

H2O
H2O Cl H2O
H2O Cl
Co Cl2 . 2H2O
Co Cl . 32 H2O
H2O H2O
H2O H2O Cl
H2O
Tetraaquadichloridocobalt(II
I) chloride dihydrate
Linkage isomerism

This isomerism arises due to the presence of ambidentate ligands .

Ambidentate
ligands
CN-/ NC-
OCN-/ NCO-
SCN- /NCS-
ONO- /NO2-
Ambidentate Ligand

CN- -
M M NC CN
C-donor Cyanido
atom

N-donor isocyanido
atom
Example

1. [Pt (NH3)2 (NO2)2]

[Pt (NH3)2 (ONO)2]
[Pt (NH3)2 (NO2)(ONO)]

Pt ONO (O donor atom)

NO2– is an Ambidentate ligand
Pt NO2 (N donor atom)

2. [Co(NH3)5(CN)]SO4
[Co(NH3)5(NC)]SO4
Coordination isomerism

This isomerism arises due to the exchange of ligands between

complex cation and complex anion.

Example

[Co(NH3)4] [Co(Cl)4]
Example

[Co(NH3)6][Cr(CN)6]

[Co(NH3)5CN] [Cr(CN)5( NH3)]

[Co(NH3)4(CN)2][Cr(CN)4(NH3)2]

[Co(NH3)3(CN)3][Cr(CN)3(NH3)3]

[Co(NH3)2(CN)4][Cr(CN)2(NH3)4]

[Co(NH3)(CN)5][Cr(CN) (NH3)5]

[Co (CN)6][Cr(NH3)6]
[Co(NH3)6][Cr(CN)6]
Example

+3 -3
NH3 CN-

NH3 NH3 CN- CN-

Co Cr

NH3 NH3 CN- CN-

NH3 CN-

Hexaamminecobalt(III)
Hexacyanocobaltate(III) Hexacyanochromate(III)
Hexaamminechromium(III)
Trick

No of coordination Isomers = C.N.(For different CMA)

= C.N./2 (For identical CMA)

**For Only mono dentate ligands

Example

[Pt(NH3)4] [Zn(Cl)4]

[Ag(NH3)2] [Ag(CN)2]