MCQMediumJEE 2025Ligands & Coordination Number

JEE Chemistry 2025 Question with Solution

Identify the coordination complexes in which the central metal ion has a d4d^4 configuration.

  • A

    (C) and (E) only

  • B

    (B), (C) and (D) only

  • C

    (B) and (D) only

  • D

    (A), (B) and (E) only

Answer

Correct answer:C

Step-by-step solution

Standard Method

Given: We need to identify the coordination complexes in which the central metal ion has a d4d^4 configuration.

Find: The correct option containing the complexes with central metal ions of configuration d4d^4.

To identify the coordination complexes in which the central metal ion has a d4d^4 configuration, examine the electronic configuration of the central metal ions in each complex.

For (A) [FeO4]2[FeO_4]^{2-}: iron is in the +6+6 oxidation state. The electronic configuration of Fe is [Ar]3d64s2[Ar] \, 3d^6 4s^2. In the +6+6 state, it loses 66 electrons, leaving a d2d^2 configuration.

Therefore, this does not match d4d^4.

For (B) [Mn(CN)6]3[Mn(CN)_6]^{3-}: manganese is in the +3+3 oxidation state. The electronic configuration of Mn is [Ar]3d54s2[Ar] \, 3d^5 4s^2. With a +3+3 charge, it loses 33 electrons, resulting in a d4d^4 configuration.

Therefore, this matches d4d^4.

For (C) [Fe(CN)6]3[Fe(CN)_6]^{3-}: iron is in the +3+3 oxidation state. The configuration of Fe is [Ar]3d64s2[Ar] \, 3d^6 4s^2. Losing 33 electrons leaves a d5d^5 configuration.

Therefore, this does not match d4d^4.

For (D) Cr2(OC(Me)4(H2O)2Cr_2(O - C(Me)_4(H_2O)_2: each Cr is in the +2+2 oxidation state. The configuration of Cr is [Ar]3d54s1[Ar] \, 3d^5 4s^1. Losing 22 electrons results in a d4d^4 configuration.

Therefore, this matches d4d^4.

For (E) [NiF6]2[NiF_6]^{2-}: nickel is in the +4+4 oxidation state. The configuration of Ni is [Ar]3d84s2[Ar] \, 3d^8 4s^2. Losing 44 electrons results in a d6d^6 configuration.

Therefore, this does not match d4d^4.

So, the complexes with d4d^4 configuration are (B) and (D) only.

Therefore, the correct option is C.

Oxidation State Analysis

Given: We must determine which listed complexes have a central metal ion with a d4d^4 electronic configuration.

Find: Which combination of complexes corresponds to d4d^4.

A d4d^4 configuration means the metal ion has 44 electrons in the dd-orbitals after accounting for its oxidation state.

  • (A) [FeO4]2[FeO_4]^{2-} gives iron in a state that leads to d2d^2, so it is not correct.
  • (B) [Mn(CN)6]3[Mn(CN)_6]^{3-} contains Mn3+Mn^{3+}, which is d4d^4, so it is correct.
  • (C) [Fe(CN)6]3[Fe(CN)_6]^{3-} contains Fe3+Fe^{3+}, which is d5d^5, so it is not correct.
  • (D) chromium complex has chromium in a state leading to d4d^4, so it is correct.
  • (E) [NiF6]2[NiF_6]^{2-} does not give a d4d^4 configuration, so it is not correct.

Thus, only (B) and (D) satisfy the required condition.

The correct option is C.

Common mistakes

  • Assuming the complex charge directly gives the metal ion configuration without first calculating the oxidation state. This is incorrect because ligand charges must be accounted for before determining the dd-electron count. Always find the oxidation state first, then write the metal ion configuration.

  • Using the neutral atom configuration instead of the ion configuration. This is wrong because d4d^4 refers to the central metal ion in the complex, not the free atom. Remove electrons according to the oxidation state before counting dd electrons.

  • Confusing ligand field strength with the basic dd-electron count. Strong-field and weak-field ligands affect spin arrangement, but the value d4d^4 depends on oxidation state and atomic configuration. First determine the ion's electron count, then think about pairing if needed.

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