Werner Theory 1

 In 1893, Alfred Werner founded the modern theory on

Coordination or Complex Compounds.

 Werner Theory basically explains the structure and formation

of complex compounds.

Werner Theory 2
 The important postulates of Werner’s theory are

The central metal or the metal atoms in coordination compounds

show two types of valencies

1. Primary valency or Ionisable valency

2. Secondary valency or Non-Ionisable valency

 Primary valency relates to the “Oxidation state” of metal atom.

 Secondary valency relates to the “ Coordination number” of

metal atom.

Werner Theory 3
 Metal atom works towards satisfying both its primary and
secondary valencies.

 A negative ion satisfies the primary valency.

 A negative ion or neutral molecules satisfy the secondary

valencies.

 The molecules or ions that satisfy secondary valencies are

called Ligands.

Werner Theory 4
 Ligands have unshared pair of electrons. The unshared pair of
electrons are donated to central metal ion or atom in
compounds and such compounds are called complex
compounds.

Werner Theory 5
 Primary valencies are non-directional in nature.
 Secondary valencies are directional in nature.

 Secondary valencies point towards a fixed position in space.

This is the reason behind the definite geometry of the complex
compounds.
 For Example
◦ Let us consider the case of a metal atom having 6 secondary
valencies,those arrange octahedrally around the central metal atom.
◦ If the metal atom has 4 secondary valencies,those arrange in either
tetrahedral or square planar arrangement around the central metal ion.

Werner Theory 6
 Werner theory is responsible for the formation of various
cobalt amines .
1- [Co(NH3)6]Cl3 :

Werner Theory 7
 Explanation of structure of [Co(NH3)6]Cl3 :
 Primary valency or Oxidation No. = 3
 Secondary valency or Coordination No. =6

 Dotted lines show Primary valency.

 Solid lines show Secondary valency.

 Cobalt has coordination no. of 6 and NH3 molecules satisfy all

the 6 secondary valencies and chloride ions satisfy the 3
primary valency.

Werner Theory 8
2- Structure of [CoCl(NH3)5]Cl2

Werner Theory 9
 Structures of [CoCl2(NH3)4]Cl and [CoCl3(NH3)3]

Werner Theory 10
  Examples
1. [CO(NH3)6] Cl3
x+6(0)=+3
x=+3
So, the oxidation no. of Co is +3.

2. K[AuCl4]
K(+1)Au(x)Cl4(-1)=0
1+x+4(-1)=0
x+(-3)=0
x=+3
So, the oxidation no. of Au is +3.

Werner Theory 11
 Examples
3. [Co(NH3)6]Cl3 :
x+(0)6+3(-1)=0
x-3=0
x=+3
So, the oxidation no. of Co is +3.

4. [Fe(CN)6]3−

x+6(-1)= -3
x=-3+6
x=+3
So, the Oxidation no. of Fe is +3.

Werner Theory 12
 Examples
5. K3[Cu(CN)4]
(+3)+x+4(-1)=0
+3+x-4=0
x-1=0
x=+1
So, the oxidation no. of Cu is +1.

6. [Ni[CO)4]

x+4(0)=0
x=0
SO, the oxidation no. of Ni is 0.

Werner Theory 13
 Werner also turned his attention towards the geometrical
arrangements of the coordinated groups around the central ion
and was successful in explaining the geometrical isomerism of
these compounds.
 When coordination no. is 4 of central metal atom there are two
possible structure
 Tetrahedral
 Square planar
 When coordination no. is 6 of central metal atom there are
three possible structure
 Planar ( 3 possible isomers)
 Trigonal prism (3 possible isomers)
 Octahedral ( 2 possible isomers)

Werner Theory 14
 Example
 [PtCl2(NH3)2]
 In this complex the coordination no. of metal is 4, Werner
found that it existed in two isomeric forms, cis and trans. This
shows that all the four ligands lie in the same plane. Therefore
the structure should be square planar or tetrahedral.

Werner Theory 15
 These are the following defects of Werner’s theory

 It could not explain the inability of all elements to form coordination

compounds.

 It could not explain the directional properties of bonds in various

coordination compounds.

 It does not explain the color of coordination compounds.

 It does not explain the magnetic and spectral properties shown by

coordination compounds.

Werner Theory 16