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Questions
Explain on the basis of valence bond theory that [Ni(CN)4]2− ion with square planar structure is diamagnetic and the [NiCl4]2− ion with tetrahedral geometry is paramagnetic.
Explain on the basis of valence bond theory, the experimental finding that [Ni(CN)4]2− ion with a square planar structure is diamagnetic and the [Ni(Cl)4]2− ion with tetrahedral geometry is paramagnetic.
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Solution
Nickel in [Ni(CN)4]2− is in the +2 oxidation state, i.e., nickel is present as Ni2+ ion and dsp2 hybrid orbitals.
| [Ni(CN)4]2− | Ni(28): 4s2 3d8 |
| Ni2+(28): 4s0 3d8 |
CN− is a strong field ligand, so it causes the pairing of electrons.
The strong ligand CN− facilitates electron pairing. The complex is diamagnetic because it contains no unpaired electrons.
In [NiCl4]2−, the formation of the above complex can be explained by hybridization. Ni in the above compound is in the +2 oxidation state, i.e., Ni2+.
As Cl− is a weak ligand, pairing of electrons does not take place. sp3 hybridisation of orbitals takes place, giving rise to tetrahedral geometry. As there are two unpaired electrons in the complex, it is paramagnetic.
It is paramagnetic due to the presence of unpaired electrons.
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