Explain on the basis of valence bond theory that

Question:

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.

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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