The correct statement among the following is:
- $\mathrm{Ni}(\mathrm{CO})_{4}$ and $\left[\mathrm{Ni}(\mathrm{CN})_{4}\right]^{2-}$ are diamagnetic and $\left[\mathrm{NiCl}_{4}\right]^{2-}$ is paramagnetic.
- $\mathrm{Ni}(\mathrm{CO})_{4}$ and $\left[\mathrm{NiCl}_{4}\right]^{2-}$ are diamagnetic and $\left[\mathrm{Ni}(\mathrm{CN})_{4}\right]^{2-}$ is paramagnetic.
- $\left[\mathrm{Ni}(\mathrm{CN})_{4}\right]^{2-}$ and $\left[\mathrm{NiCl}_{4}\right]^{2-}$ are diamagnetic and $\mathrm{Ni}(\mathrm{CO})_{4}$ is paramagnetic.
- $\mathrm{Ni}(\mathrm{CO})_{4}$ is diamagnetic and $\left[\mathrm{NiCl}_{4}\right]^{2-}$ and $\left[\mathrm{Ni}(\mathrm{CN})_{4}\right]^{2-}$ are paramagnetic.
Solution
In $[Ni(CN)_4]^{2-}$, Nickel is in $+2$ oxidation state with configuration $[Ar]3d^8$. $CN^-$ is a strong field ligand, causing pairing of the two unpaired electrons in $3d$ orbitals. It is $dsp^2$ hybridized (square planar) and diamagnetic.
In $[NiCl_4]^{2-}$, Nickel is in $+2$ oxidation state with configuration $[Ar]3d^8$. $Cl^-$ is a weak field ligand and cannot cause pairing of electrons. It has two unpaired electrons in $3d$ orbitals, making it $sp^3$ hybridized (tetrahedral) and paramagnetic.
Therefore, $Ni(CO)_4$ and $[Ni(CN)_4]^{2-}$ are diamagnetic, while $[NiCl_4]^{2-}$ is paramagnetic.
Asked in: JEE Main 2026 (28 Jan Shift 1)