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JEE Chemistry 2025 Question with Solution

In which of the following complexes the CFSE, Δ0\Delta_0 will be equal to zero?

  • A

    [Fe(NH3)6]Br2[Fe(NH_3)_6]Br_2

  • B

    [Fe(en)3]Cl3[Fe(en)_3]Cl_3

  • C

    K4[Fe(CN)6]K_4[Fe(CN)_6]

  • D

    K3[Fe(SCN)6]K_3[Fe(SCN)_6]

Answer

Correct answer:D

Step-by-step solution

Standard Method

Given: Four octahedral iron complexes are given.

Find: Which complex has CFSE = 00.

CFSE depends on the oxidation state of iron, its dd-electron configuration, and whether the complex is high spin or low spin.

From the solution:

  1. [Fe(NH3)6]Br2[Fe(NH_3)_6]Br_2
  • Oxidation state of FeFe is +2+2
  • Configuration is d6d^6
  1. [Fe(en)3]Cl3[Fe(en)_3]Cl_3
  • Oxidation state of FeFe is +3+3
  • Configuration is d5d^5
  1. K4[Fe(CN)6]K_4[Fe(CN)_6]
  • Oxidation state of FeFe is +2+2
  • Configuration is d6d^6
  1. K3[Fe(SCN)6]K_3[Fe(SCN)_6]
  • Oxidation state of FeFe is +3+3
  • Configuration is d5d^5

Using d-electron configuration and spin state

For an octahedral complex, CFSE becomes zero for a high-spin d5d^5 configuration because the electrons are distributed as:

t2g3eg2t_{2g}^3 e_g^2

Hence the stabilization and destabilization contributions cancel.

As stated in the solution, in [Fe(SCN)6]3[Fe(SCN)_6]^{3-}, iron is Fe3+Fe^{3+}, so it is d5d^5. Since SCNSCN^- acts here to give a high-spin arrangement, the distribution is:

t2g3eg2t_{2g}^3 e_g^2

Therefore, CFSE is zero.

Thus, the complex K3[Fe(SCN)6]K_3[Fe(SCN)_6] has CFSE = 00. The correct option is D.

Common mistakes

  • Assuming every d5d^5 complex has zero CFSE. This is wrong because only the high-spin octahedral d5d^5 case gives zero CFSE; low-spin d5d^5 does not. Always check ligand strength and spin state.

  • Ignoring oxidation state while counting dd electrons. This is wrong because CFSE depends on the metal ion configuration, not neutral iron. First find the oxidation state of FeFe, then determine whether it is d5d^5 or d6d^6.

  • Treating CNCN^- and SCNSCN^- complexes similarly. This is wrong because ligands differ in field strength, so the electron arrangement can change. Use the ligand nature along with oxidation state before concluding CFSE.

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