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Coordination Compounds question

2008 · Shift 0 · Q19
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Coordination Compounds question

2008 · Shift 0 · Q19

JEE MainChemistryCoordination CompoundsMCQ+4 / −1
In which of the following octahedral complexes of Co (at. no. 27), will the magnitude of Δo\Delta _oΔo​ be the highest?
  1. A
    [Co(CN)6]3−[Co(CN)_6]^{3-}[Co(CN)6​]3−
  2. B
    [Co(C2O4)3]3−[Co(C_2O_4)_3]^{3-}[Co(C2​O4​)3​]3−
  3. C
    [Co(H2O)6]3+[Co(H_2O)_6]^{3+}[Co(H2​O)6​]3+
  4. D
    [Co(NH3)6]3+[Co(NH_3)_6]^{3+}[Co(NH3​)6​]3+
View written solutionFree

Correct answer: A

  1. Find the oxidation state and d-configuration of Co in each complex

For all given complexes, cobalt is in the +3 oxidation state:

  • [Co(CN)6]3−[Co(CN)_6]^{3-}[Co(CN)6​]3−: x+6(−1)=−3⇒x=+3x + 6(-1) = -3 \Rightarrow x = +3x+6(−1)=−3⇒x=+3
  • [Co(C2O4)3]3−[Co(C_2O_4)_3]^{3-}[Co(C2​O4​)3​]3−: x+3(−2)=−3⇒x=+3x + 3(-2) = -3 \Rightarrow x = +3x+3(−2)=−3⇒x=+3
  • [Co(H2O)6]3+[Co(H_2O)_6]^{3+}[Co(H2​O)6​]3+: H2OH_2OH2​O is neutral, so x=+3x = +3x=+3
  • [Co(NH3)6]3+[Co(NH_3)_6]^{3+}[Co(NH3​)6​]3+: NH3NH_3NH3​ is neutral, so x=+3x = +3x=+3

So in every case, the metal ion is Co3+Co^{3+}Co3+.

Cobalt has atomic number 272727:

Co:[Ar]3d74s2Co: [Ar]3d^74s^2Co:[Ar]3d74s2

Thus,

Co3+:[Ar]3d6Co^{3+} : [Ar]3d^6Co3+:[Ar]3d6

Since the metal ion is the same in all complexes, the magnitude of Δo\Delta_oΔo​ depends mainly on the nature of the ligand.


  1. Use spectrochemical series

The octahedral crystal field splitting increases with ligand field strength.

Relevant part of the spectrochemical series is:

C2O42−<H2O<NH3<CN−C_2O_4^{2-} < H_2O < NH_3 < CN^-C2​O42−​<H2​O<NH3​<CN−

Thus, among the given ligands:

  • CN−CN^-CN− is the strongest field ligand
  • NH3NH_3NH3​ is stronger than H2OH_2OH2​O
  • Oxalate (C2O42−)\left(C_2O_4^{2-}\right)(C2​O42−​) is weaker than both H2OH_2OH2​O and NH3NH_3NH3​

Therefore,

Δo([Co(CN)6]3−)>Δo([Co(NH3)6]3+)>Δo([Co(H2O)6]3+)>Δo([Co(C2O4)3]3−)\Delta_o([Co(CN)_6]^{3-}) > \Delta_o([Co(NH_3)_6]^{3+}) > \Delta_o([Co(H_2O)_6]^{3+}) > \Delta_o([Co(C_2O_4)_3]^{3-})Δo​([Co(CN)6​]3−)>Δo​([Co(NH3​)6​]3+)>Δo​([Co(H2​O)6​]3+)>Δo​([Co(C2​O4​)3​]3−)


  1. Evaluate the options
  • A: [Co(CN)6]3−[Co(CN)_6]^{3-}[Co(CN)6​]3− — strongest ligand CN−CN^-CN−, so largest Δo\Delta_oΔo​
  • B: [Co(C2O4)3]3−[Co(C_2O_4)_3]^{3-}[Co(C2​O4​)3​]3− — oxalate is weaker, so not highest
  • C: [Co(H2O)6]3+[Co(H_2O)_6]^{3+}[Co(H2​O)6​]3+ — weaker than NH3NH_3NH3​ and CN−CN^-CN−
  • D: [Co(NH3)6]3+[Co(NH_3)_6]^{3+}[Co(NH3​)6​]3+ — strong, but still weaker than CN−CN^-CN−

Hence, the highest value of Δo\Delta_oΔo​ is for:

[Co(CN)6]3−\boxed{[Co(CN)_6]^{3-}}[Co(CN)6​]3−​

So, option A is correct.

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