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JEE Advanced 2019 Paper 2 · Chemistry · Coordination Compounds · medium

Consider the nickel(II) complexes [NiCl4]^2-, [Ni(CN)4]^2- and Ni(CO)4 (atomic number of Ni =28).

One or more options correct

Consider the nickel(II) complexes [NiCl4]2−\mathrm{[NiCl_4]^{2-}}, [Ni(CN)4]2−\mathrm{[Ni(CN)_4]^{2-}} and Ni(CO)4\mathrm{Ni(CO)_4} (atomic number of Ni =28=28). The correct statement(s) is(are)
  1. A. [NiCl4]2−\mathrm{[NiCl_4]^{2-}} is tetrahedral and paramagnetic with two unpaired electrons
  2. B. [Ni(CN)4]2−\mathrm{[Ni(CN)_4]^{2-}} is square planar and diamagnetic
  3. C. Ni(CO)4\mathrm{Ni(CO)_4} is tetrahedral and paramagnetic because Ni is present in the zero oxidation state with a d8s2d^8s^2 configuration
  4. D. [NiCl4]2−\mathrm{[NiCl_4]^{2-}} and [Ni(CN)4]2−\mathrm{[Ni(CN)_4]^{2-}} have the same spin-only magnetic moment
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Answer: A, B

Ni(II) is d8d^8. With the weak-field ligand Cl−\mathrm{Cl^-} the complex [NiCl4]2−\mathrm{[NiCl_4]^{2-}} is sp3sp^3 tetrahedral; in the tetrahedral field the d8d^8 configuration e4t24e^4t_2^4 leaves two unpaired electrons, so it is paramagnetic and (A) is correct. The strong-field ligand CN−\mathrm{CN^-} forces pairing of all eight electrons in four orbitals, freeing one 3d3d orbital for dsp2dsp^2 hybridisation, so [Ni(CN)4]2−\mathrm{[Ni(CN)_4]^{2-}} is square planar and diamagnetic and (B) is correct. In Ni(CO)4\mathrm{Ni(CO)_4} the strong-field CO ligands push the two 4s4s electrons into 3d3d, giving 3d103d^{10} nickel(0); it is sp3sp^3 tetrahedral but has no unpaired electron, so it is diamagnetic and (C) is wrong. Since [NiCl4]2−\mathrm{[NiCl_4]^{2-}} has two unpaired electrons (μ=8≈2.83\mu=\sqrt{8}\approx2.83 BM) while [Ni(CN)4]2−\mathrm{[Ni(CN)_4]^{2-}} has none, (D) is wrong.
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