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.

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Solution

Ni is in the +2 oxidation state i.e., in d⁸ configuration.

There are 4 CN⁻ ions. Thus, it can either have a tetrahedral geometry or square planar geometry. Since CN⁻ ion is a strong field ligand, it causes the pairing of unpaired 3d electrons.

It now undergoes dsp² hybridization. Since all electrons are paired, it is diamagnetic.

In case of [NiCl₄]²⁻, Cl⁻ ion is a weak field ligand. Therefore, it does not lead to the pairing of unpaired 3d electrons. Therefore, it undergoes sp³ hybridization.

Since there are 2 unpaired electrons in this case, it is paramagnetic in nature.

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