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Q5.4:
What is meant by unidentate, didentate and ambidentate ligands? Give two examples for each.

Solution :

1. Definition of Ligands and Denticity

In coordination chemistry, a ligand is an ion or molecule attached to a central metal atom or ion to form a coordination complex. The denticity of a ligand refers to the number of donor atoms through which the ligand coordinates to the central metal atom. Ligands are classified based on the number of donor atoms they utilize to form coordinate covalent bonds.

2. Classification of Ligands

Ligand Type Definition Examples
Unidentate Ligands that coordinate to the central metal atom through only one donor atom. $Cl^-$, $NH_3$
Didentate Ligands that have two donor atoms and can coordinate to the central metal atom through both simultaneously, forming a chelate ring. $H_2N-CH_2-CH_2-NH_2$ (en), $C_2O_4^{2-}$ (ox)
Ambidentate Monodentate ligands which have two different donor atoms, but only one of them forms a coordinate bond at a time. $NO_2^-$, $SCN^-$

3. Analytical Breakdown of Ligand Types

A. Unidentate Ligands

These ligands possess a single lone pair of electrons available for donation. They form one coordinate bond per ligand molecule.

  • Chloride ion ($Cl^-$): Donates electron density from a lone pair on the chlorine atom.
  • Ammine ($NH_3$): Donates the lone pair of electrons from the nitrogen atom to the metal orbital.

B. Didentate (Bidentate) Ligands

These ligands possess two distinct donor sites. When both sites attach to the same metal, they form a heterocyclic ring structure known as a chelate [Per Chelate Effect].

  • Ethane-1,2-diamine ($en$): $H_2N-CH_2-CH_2-NH_2$. Both nitrogen atoms act as donor sites.
  • Oxalate ion ($ox^{2-}$): $C_2O_4^{2-}$. Two oxygen atoms donate electron pairs to the metal center.

C. Ambidentate Ligands

These exhibit linkage isomerism because they possess multiple potential donor atoms, though sterics or electronic factors usually dictate which atom binds.

  • Nitrite ion ($NO_2^-$): Can bind via Nitrogen (nitro, $-NO_2$) or via Oxygen (nitrito, $-ONO$).
  • Thiocyanate ion ($SCN^-$): Can bind via Sulfur (thiocyanato-S, $-SCN$) or via Nitrogen (isothiocyanato-N, $-NCS$).

4. Structural Visualization of Linkage

Nitro Linkage (M-NOâ‚‚) M N-Oâ‚‚ Nitrito Linkage (M-ONO) M O-NO

Final Solution: Unidentate ligands (e.g., $Cl^-$, $NH_3$) use one donor atom; Didentate ligands (e.g., $en$, $ox^{2-}$) use two donor atoms to form rings; Ambidentate ligands (e.g., $NO_2^-$, $SCN^-$) contain two potential donor sites but coordinate through only one at a time.


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