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Coordination Compounds question

2016 · 9 Apr · Shift 1 · Q11
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Coordination Compounds question

2016 · 9 Apr · Shift 1 · Q11

JEE MainChemistryCoordination CompoundsMCQ+4 / −1
Identify the correct trend given below : (Atomic No.=Ti : 22, Cr : 24 and Mo : 42)
  1. A
    Δ\DeltaΔ o of [Cr(H2O)6]2+[Cr(H_2O)_6]^{2+}[Cr(H2​O)6​]2+ > [Mo(H2O)6]2+[Mo(H_2O)_6]^{2+}[Mo(H2​O)6​]2+ and Δ\DeltaΔ o of [Ti(H2O)6]3+[Ti(H_2O)_6]^{3+}[Ti(H2​O)6​]3+ > [Ti(H2O)6]2+[Ti(H_2O)_6]^{2+}[Ti(H2​O)6​]2+
  2. B
    Δ\DeltaΔ o of [Cr(H2O)6]2+[Cr(H_2O)_6]^{2+}[Cr(H2​O)6​]2+ > [Mo(H2O)6]2+[Mo(H_2O)_6]^{2+}[Mo(H2​O)6​]2+ and Δ\DeltaΔ o of [Ti(H2O)6]3+[Ti(H_2O)_6]^{3+}[Ti(H2​O)6​]3+ < [Ti(H2O)6]2+[Ti(H_2O)_6]^{2+}[Ti(H2​O)6​]2+
  3. C
    Δ\DeltaΔ o of [Cr(H2O)6]2+[Cr(H_2O)_6]^{2+}[Cr(H2​O)6​]2+ < [Mo(H2O)6]2+[Mo(H_2O)_6]^{2+}[Mo(H2​O)6​]2+ and Δ\DeltaΔ o of [Ti(H2O)6]3+[Ti(H_2O)_6]^{3+}[Ti(H2​O)6​]3+ > [Ti(H2O)6]2+[Ti(H_2O)_6]^{2+}[Ti(H2​O)6​]2+
  4. D
    Δ\DeltaΔ o of [Cr(H2O)6]2+[Cr(H_2O)_6]^{2+}[Cr(H2​O)6​]2+ < [Mo(H2O)6]2+[Mo(H_2O)_6]^{2+}[Mo(H2​O)6​]2+ and Δ\DeltaΔ o of [Ti(H2O)6]3+[Ti(H_2O)_6]^{3+}[Ti(H2​O)6​]3+ < [Ti(H2O)6]2+[Ti(H_2O)_6]^{2+}[Ti(H2​O)6​]2+
View written solutionFree

Correct answer: C

  1. We need the trend in octahedral crystal field splitting, Δo\Delta_oΔo​, for aqua complexes.

    For a given ligand (H2OH_2OH2​O here), Δo\Delta_oΔo​ generally depends on:

    • oxidation state of the metal: higher oxidation state ⇒\Rightarrow⇒ larger Δo\Delta_oΔo​
    • principal quantum number / row of transition metal: typically 3d<4d<5d3d < 4d < 5d3d<4d<5d for comparable ions, so heavier congeners usually give larger splitting.

  1. Compare [Ti(H2O)6]3+[Ti(H_2O)_6]^{3+}[Ti(H2​O)6​]3+ and [Ti(H2O)6]2+[Ti(H_2O)_6]^{2+}[Ti(H2​O)6​]2+

    Both have the same metal and same ligand, only oxidation state differs.

    • In [Ti(H2O)6]3+[Ti(H_2O)_6]^{3+}[Ti(H2​O)6​]3+, metal is Ti3+Ti^{3+}Ti3+
    • In [Ti(H2O)6]2+[Ti(H_2O)_6]^{2+}[Ti(H2​O)6​]2+, metal is Ti2+Ti^{2+}Ti2+

    Since higher oxidation state increases metal-ligand attraction and shortens bond length, we get Δo([Ti(H2O)6]3+)>Δo([Ti(H2O)6]2+)\Delta_o\big([Ti(H_2O)_6]^{3+}\big) > \Delta_o\big([Ti(H_2O)_6]^{2+}\big)Δo​([Ti(H2​O)6​]3+)>Δo​([Ti(H2​O)6​]2+)

    So any option saying [Ti(H2O)6]3+<[Ti(H2O)6]2+[Ti(H_2O)_6]^{3+} < [Ti(H_2O)_6]^{2+}[Ti(H2​O)6​]3+<[Ti(H2​O)6​]2+ is incorrect.

    Hence options B and D are eliminated.


  1. Compare [Cr(H2O)6]2+[Cr(H_2O)_6]^{2+}[Cr(H2​O)6​]2+ and [Mo(H2O)6]2+[Mo(H_2O)_6]^{2+}[Mo(H2​O)6​]2+

    These are both M2+M^{2+}M2+ aqua complexes, but:

    • CrCrCr is a 3d3d3d element
    • MoMoMo is a 4d4d4d element

    For similar oxidation state and ligand, 4d4d4d metals usually have larger crystal field splitting than 3d3d3d metals because their orbitals are more diffuse and overlap better with ligands.

    Therefore, Δo([Mo(H2O)6]2+)>Δo([Cr(H2O)6]2+)\Delta_o\big([Mo(H_2O)_6]^{2+}\big) > \Delta_o\big([Cr(H_2O)_6]^{2+}\big)Δo​([Mo(H2​O)6​]2+)>Δo​([Cr(H2​O)6​]2+)

    or equivalently, Δo([Cr(H2O)6]2+)<Δo([Mo(H2O)6]2+)\Delta_o\big([Cr(H_2O)_6]^{2+}\big) < \Delta_o\big([Mo(H_2O)_6]^{2+}\big)Δo​([Cr(H2​O)6​]2+)<Δo​([Mo(H2​O)6​]2+)


  1. Match with the options

    We need:

    • Δo([Cr(H2O)6]2+)<Δo([Mo(H2O)6]2+)\Delta_o([Cr(H_2O)_6]^{2+}) < \Delta_o([Mo(H_2O)_6]^{2+})Δo​([Cr(H2​O)6​]2+)<Δo​([Mo(H2​O)6​]2+)
    • Δo([Ti(H2O)6]3+)>Δo([Ti(H2O)6]2+)\Delta_o([Ti(H_2O)_6]^{3+}) > \Delta_o([Ti(H_2O)_6]^{2+})Δo​([Ti(H2​O)6​]3+)>Δo​([Ti(H2​O)6​]2+)

    This corresponds to Option C.


  1. Final answer

    C\boxed{\text{C}}C​

This matches the stored correct answer.

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