Werner's Theory: Structure Of Coordination Compounds

This topic explains about Werner’s theory: Structure of coordination compounds. A coordination compound is a complex compound which contains a metal bonded to ligands. A ligand can be an atom, an ion or a molecule that donates electrons to the metal. They were known since the 18th century but no theory was developed till that time which could explain for the properties of these compounds. In the year 1898, Alfred Werner proposed Werner’s theory explaining the structure of coordination compounds. He carried out a series of experiments on cobalt (III) chloride and ammonia. Upon addition of silver nitrate solution, he observed that some of the chloride ions precipitated as silver chloride. Further, he also observed that the amount of silver chloride formed was related to the number of ammonia molecules bound to the cobalt (III) chloride. For example, On adding silver nitrate to CoCl3·6NH3, all the three ions of chloride converted to silver chloride. However, when silver nitrate was added to CoCl3·5NH3, the number of moles of silver chloride formed was equal to two. On treating CoCl3·4NH3 with silver nitrate, one mole of silver chloride was formed. On the basis of this observation, the following theory was postulated by Werner:

  • The central metal atom in a coordination compound exhibits two types of valencies (linkages) – primary and secondary.
  • Primary valences are generally ionizable and are satisfied by negative ions.
  • The secondary valences are non-ionizable. These are generally satisfied by negative ions or neutral molecules. The secondary valence is fixed for a metal and is equal to the coordination number.
  • The ions bounded by the secondary linkages to the metal exhibit characteristic spatial arrangements corresponding to different coordination numbers.

Such spatial arrangements are now known as coordination polyhedra. The species within the square brackets are called coordination entities or complexes and the ions outside the square brackets are known as counter ions.

Limitations of Werner’s Theory:

  1. It does not explain the color, and the magnetic and optical properties shown by coordination compounds
  2. It failed to explain why all elements don’t form coordination compounds
  3. It failed to explain the directional properties of bonds in coordination compounds

For detailed discussions on Werner’s theory, download BYJU’S – the learning app.


Practise This Question

In K4Fe(CN)6