MCQEasyJEE 2025Crystal Field Theory

JEE Chemistry 2025 Question with Solution

The correct order of [FeF6]3[FeF_6]^{3-}, [CoF6]3[CoF_6]^{3-}, [Ni(CO)4][Ni(CO)_4] and [Ni(CN)4]2[Ni(CN)_4]^{2-} complex species based on the number of unpaired electrons present is:

  • A

    [FeF6]3>[CoF6]3>[Ni(CN)4]2>[Ni(CO)4][FeF_6]^{3-} > [CoF_6]^{3-} > [Ni(CN)_4]^{2-} > [Ni(CO)_4]

  • B

    [Ni(CN)4]2>[FeF6]3>[CoF6]3>[Ni(CO)4][Ni(CN)_4]^{2-} > [FeF_6]^{3-} > [CoF_6]^{3-} > [Ni(CO)_4]

  • C

    [CoF6]3>[FeF6]3>[Ni(CO)4]>[Ni(CN)4]2[CoF_6]^{3-} > [FeF_6]^{3-} > [Ni(CO)_4] > [Ni(CN)_4]^{2-}

  • D

    [FeF6]3>[CoF6]3>[Ni(CN)4]2=[Ni(CO)4][FeF_6]^{3-} > [CoF_6]^{3-} > [Ni(CN)_4]^{2-} = [Ni(CO)_4]

Answer

Correct answer:D

Step-by-step solution

Standard Method

Given: The complexes are [FeF6]3[FeF_6]^{3-}, [CoF6]3[CoF_6]^{3-}, [Ni(CO)4][Ni(CO)_4] and [Ni(CN)4]2[Ni(CN)_4]^{2-}.

Find: The correct order based on the number of unpaired electrons present.

We analyze the oxidation state, electronic configuration and ligand field strength for each complex.

  1. For [FeF6]3[FeF_6]^{3-}:
  • Iron is in the +3+3 oxidation state, so it is Fe3+Fe^{3+}.
  • Its electronic configuration is [Ar]3d5[Ar] \, 3d^5.
  • FF^- is a weak field ligand, so the complex is high spin.
  • Therefore, the number of unpaired electrons is 55.
  1. For [CoF6]3[CoF_6]^{3-}:
  • Cobalt is in the +3+3 oxidation state, so it is Co3+Co^{3+}.
  • Its electronic configuration is [Ar]3d6[Ar] \, 3d^6.
  • FF^- is a weak field ligand, so the complex is high spin.
  • Therefore, the number of unpaired electrons is 44.
  1. For [Ni(CO)4][Ni(CO)_4]:
  • Nickel is in the 00 oxidation state, so it is Ni0Ni^0.
  • The configuration is [Ar]3d84s2[Ar] \, 3d^8 \, 4s^2.
  • COCO is a strong field ligand and causes pairing of electrons.
  • Therefore, the number of unpaired electrons is 00.
  1. For [Ni(CN)4]2[Ni(CN)_4]^{2-}:
  • Nickel is in the +2+2 oxidation state, so it is Ni2+Ni^{2+}.
  • Its electronic configuration is [Ar]3d8[Ar] \, 3d^8.
  • CNCN^- is a strong field ligand and causes pairing of electrons.
  • Therefore, the number of unpaired electrons is 00.

Hence, the required order is

[FeF6]3>[CoF6]3>[Ni(CN)4]2=[Ni(CO)4][FeF_6]^{3-} > [CoF_6]^{3-} > [Ni(CN)_4]^{2-} = [Ni(CO)_4]

Therefore, the correct option is D.

Electronic Configuration Comparison

Given: The same four complexes are to be compared by unpaired electrons.

Find: Their decreasing order of unpaired electrons.

Use ligand strength directly:

  • FF^- is a weak field ligand, so [FeF6]3[FeF_6]^{3-} and [CoF6]3[CoF_6]^{3-} are high spin.
  • COCO and CNCN^- are strong field ligands, so [Ni(CO)4][Ni(CO)_4] and [Ni(CN)4]2[Ni(CN)_4]^{2-} have paired electrons.

Now compare the metal ions:

  • Fe3+:3d5Fe^{3+} : 3d^5 gives 55 unpaired electrons in high spin state.
  • Co3+:3d6Co^{3+} : 3d^6 gives 44 unpaired electrons in high spin state.
  • Both nickel complexes here have 00 unpaired electrons.

So the order is

[FeF6]3>[CoF6]3>[Ni(CN)4]2=[Ni(CO)4][FeF_6]^{3-} > [CoF_6]^{3-} > [Ni(CN)_4]^{2-} = [Ni(CO)_4]

Therefore, the correct option is D.

Common mistakes

  • Assuming that all octahedral complexes are low spin is incorrect. For [FeF6]3[FeF_6]^{3-} and [CoF6]3[CoF_6]^{3-}, FF^- is a weak field ligand, so these complexes are high spin. Always check ligand strength before counting unpaired electrons.

  • Using the neutral atom configuration instead of the metal ion configuration leads to wrong counting. First find the oxidation state of the metal, then write the correct electronic configuration such as Fe3+:3d5Fe^{3+} : 3d^5 and Co3+:3d6Co^{3+} : 3d^6.

  • Treating [Ni(CN)4]2[Ni(CN)_4]^{2-} as if it must contain unpaired electrons because nickel is 3d83d^8 is wrong. Here CNCN^- is a strong field ligand, so electron pairing occurs and the complex has no unpaired electrons.

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