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JEE Advanced 2019 Paper 1 · Chemistry · Coordination Compounds · medium

The correct statement(s) about the complexes [Ni(CO)4], [NiCl4]^2-, [Ni(CN)4]^2- and [Fe(CN)6]^4- is(are)

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The correct statement(s) about the complexes [Ni(CO)4][\mathrm{Ni(CO)_4}], [NiCl4]2−[\mathrm{NiCl_4}]^{2-}, [Ni(CN)4]2−[\mathrm{Ni(CN)_4}]^{2-} and [Fe(CN)6]4−[\mathrm{Fe(CN)_6}]^{4-} is(are)
  1. A. [Ni(CO)4][\mathrm{Ni(CO)_4}] is tetrahedral and diamagnetic.
  2. B. [NiCl4]2−[\mathrm{NiCl_4}]^{2-} is tetrahedral with two unpaired electrons.
  3. C. [Ni(CN)4]2−[\mathrm{Ni(CN)_4}]^{2-} is square planar and diamagnetic.
  4. D. [Fe(CN)6]4−[\mathrm{Fe(CN)_6}]^{4-} has a spin-only magnetic moment of about 4.9 BM4.9\ \mathrm{BM}.
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Answer: A, B, C

Count d electrons and ligand field strength. In [Ni(CO)4][\mathrm{Ni(CO)_4}] nickel is Ni(0)\mathrm{Ni(0)}, d10d^{10}, sp3sp^3 and tetrahedral; all electrons are paired, so (A) is true. In [NiCl4]2−[\mathrm{NiCl_4}]^{2-}, Ni2+\mathrm{Ni^{2+}} is d8d^8 and the weak-field chloride gives a tetrahedral geometry in which two electrons are unpaired, so μ=2⋅4=2.83\mu=\sqrt{2\cdot4}=2.83 BM; (B) is true. In [Ni(CN)4]2−[\mathrm{Ni(CN)_4}]^{2-} the strong-field cyanide forces pairing of the d8d^8 ion and dsp2dsp^2 square planar geometry, diamagnetic; (C) is true. In [Fe(CN)6]4−[\mathrm{Fe(CN)_6}]^{4-}, Fe2+\mathrm{Fe^{2+}} is d6d^6 and cyanide gives the low-spin t2g6t_{2g}^6 configuration with no unpaired electrons, so it is diamagnetic. The value 4.9 BM would be the high-spin d6d^6 case, so (D) is false.
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