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Coordination Compounds question

2020 · 7 Jan · Shift 2 · Q2
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Coordination Compounds question

2020 · 7 Jan · Shift 2 · Q2

JEE MainChemistryCoordination CompoundsMCQ+4 / −1
Among the statements(a)-(d) the incorrect ones are : (a) Octahedral CO(III) complexes with strong fields ligands have very high magnetic moments. (b) When Δ\DeltaΔ 0 < P, the d-electron configuration of Co(III) in an octahedral complex is teg4eg2t_{eg}^4e_g^2teg4​eg2​(c) Wavelength of light absorbed by [Co(en)3]3+[Co(en)_3]^{3+}[Co(en)3​]3+ is lower than that of [CoF6]3−[CoF_6]^{3-}[CoF6​]3− (d) If the Δ\DeltaΔ 0 for an octahedral complex of CO(III) is 18,000 cm-1, the Δ\DeltaΔ t for its tetrahedral complex with the same ligand be 16,000 cm-1
  1. A
    (a) and (b) only
  2. B
    (b) and (c) only
  3. C
    (c) and (d) only
  4. D
    (a) and (d) only
View written solutionFree

Correct answer: D

  1. Identify the metal ion configuration

For Co3+\mathrm{Co^{3+}}Co3+:

Co:[Ar]3d74s2\mathrm{Co}: [Ar]3d^74s^2Co:[Ar]3d74s2 Co3+:[Ar]3d6\mathrm{Co^{3+}}: [Ar]3d^6Co3+:[Ar]3d6

So all statements must be checked for an octahedral or tetrahedral d6d^6d6 system.


  1. Check statement (a)

Octahedral Co(III) complexes with strong field ligands have very high magnetic moments.

For octahedral d6d^6d6 with strong field ligands, electrons pair up in t2gt_{2g}t2g​:

t2g6eg0t_{2g}^6 e_g^0t2g6​eg0​

This is a low-spin configuration with no unpaired electrons. Hence magnetic moment is very low (actually diamagnetic, μ≈0\mu \approx 0μ≈0 BM), not very high.

So, (a) is incorrect.


  1. Check statement (b)

When Δo<P\Delta_o < PΔo​<P, the d-electron configuration of Co(III) in an octahedral complex is teg4eg2t_{eg}^4 e_g^2teg4​eg2​.

There is a typographical issue in the statement: in octahedral splitting, the lower set is t2gt_{2g}t2g​, not tegt_{eg}teg​. Interpreting it as the intended configuration:

If Δo<P\Delta_o < PΔo​<P, the complex is high spin. For octahedral d6d^6d6 high-spin configuration:

t2g4eg2t_{2g}^4 e_g^2t2g4​eg2​

That is correct for d6d^6d6.

So (b) is correct (clearly intended as t2g4eg2t_{2g}^4 e_g^2t2g4​eg2​).


  1. Check statement (c)

Wavelength of light absorbed by [Co(en)3]3+[Co(en)_3]^{3+}[Co(en)3​]3+ is lower than that of [CoF6]3−[CoF_6]^{3-}[CoF6​]3−.

Use spectrochemical series:

en>F−en > F^-en>F−

Thus,

Δo([Co(en)3]3+)>Δo([CoF6]3−)\Delta_o([Co(en)_3]^{3+}) > \Delta_o([CoF_6]^{3-})Δo​([Co(en)3​]3+)>Δo​([CoF6​]3−)

Energy absorbed is proportional to Δo\Delta_oΔo​:

E=hν=hcλE = h\nu = \frac{hc}{\lambda}E=hν=λhc​

Larger Δo\Delta_oΔo​ means larger energy, hence smaller wavelength. Therefore,

λ[Co(en)3]3+<λ[CoF6]3−\lambda_{[Co(en)_3]^{3+}} < \lambda_{[CoF_6]^{3-}}λ[Co(en)3​]3+​<λ[CoF6​]3−​

So (c) is correct.


  1. Check statement (d)

If the Δo\Delta_oΔo​ for an octahedral complex of Co(III) is 18000 cm−118000\,\text{cm}^{-1}18000cm−1, the Δt\Delta_tΔt​ for its tetrahedral complex with the same ligand is 16000 cm−116000\,\text{cm}^{-1}16000cm−1.

For the same metal ion and same ligand:

Δt≈49Δo\Delta_t \approx \frac{4}{9}\Delta_oΔt​≈94​Δo​

So,

Δt=49×18000=8000 cm−1\Delta_t = \frac{4}{9}\times 18000 = 8000\,\text{cm}^{-1}Δt​=94​×18000=8000cm−1

Not 16000 cm−116000\,\text{cm}^{-1}16000cm−1.

So (d) is incorrect.


  1. Conclusion

Incorrect statements are:

(a) and (d)(a) \text{ and } (d)(a) and (d)

Therefore, the correct option is D.

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