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NEET CHEMISTRYMedium

The complex ion that is not expected to absorb visible light is:

A

[Ni(CN)₄]²⁻

B

[Cr(NH₃)₆]³⁺

C

[Fe(H₂O)₆]²⁺

D

[Ni(H₂O)₆]²⁺

Step-by-Step Solution

The absorption of visible light in coordination compounds is primarily due to d-d transitions of unpaired electrons.

  1. [Ni(CN)₄]²⁻: Nickel is in the +2 oxidation state (3d83d^8). The cyanide ion (CNCN^-) is a strong field ligand. As per Valence Bond Theory and Crystal Field Theory, in a coordination number of 4 with a strong ligand, Ni2+Ni^{2+} forms a square planar complex involving dsp² hybridisation. The strong field causes all 8 d-electrons to pair up in the lower energy orbitals (dxy,dyz,dzx,dz2d_{xy}, d_{yz}, d_{zx}, d_{z^2}). Since there are no unpaired electrons and the crystal field splitting energy (Δ\Delta ) is very large (often shifting absorption to the UV region), it is the least expected to absorb in the visible region compared to the others .
  2. [Ni(H₂O)₆]²⁺: Contains H2OH_2O (weak field ligand). It is an outer orbital octahedral complex with 2 unpaired electrons (3d83d^8). It is green in colour .
  3. [Cr(NH₃)₆]³⁺: Chromium is in the +3 oxidation state (3d33d^3). It has 3 unpaired electrons and exhibits d-d transitions, absorbing visible light.
  4. [Fe(H₂O)₆]²⁺: Iron is in the +2 oxidation state (3d63d^6). With a weak field ligand, it is high spin with 4 unpaired electrons, absorbing visible light (pale green).

Therefore, the diamagnetic complex [Ni(CN)4]2[Ni(CN)_4]^{2-} is the correct answer.

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