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JEE Advanced 2021 Paper 2 · Chemistry · Coordination Compounds · medium

Spin-only magnetic moments are to be used where needed. The atomic numbers are Fe=26, Co=27, Ni=28. The correct statement(s) about the following…

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Spin-only magnetic moments are to be used where needed. The atomic numbers are Fe=26\mathrm{Fe}=26, Co=27\mathrm{Co}=27, Ni=28\mathrm{Ni}=28. The correct statement(s) about the following coordination species is/are (en = ethane-1,2-diamine)
  1. A. [Fe(CN)6]3−[\mathrm{Fe(CN)_6}]^{3-} has a spin-only magnetic moment of 3\sqrt3 BM
  2. B. [NiCl4]2−[\mathrm{NiCl_4}]^{2-} is tetrahedral with a spin-only magnetic moment of 8\sqrt8 BM
  3. C. [Co(en)2Cl2]+[\mathrm{Co(en)_2Cl_2}]^{+} exists as exactly three stereoisomers
  4. D. [CoF6]3−[\mathrm{CoF_6}]^{3-} is diamagnetic because F−\mathrm{F^-} is a strong-field ligand
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Answer: A, B, C

A: Fe3+\mathrm{Fe^{3+}} is d5d^5 and CN−\mathrm{CN^-} is a strong-field ligand, so the configuration is t2g5t_{2g}^5 with one unpaired electron and μ=1(1+2)=3\mu=\sqrt{1(1+2)}=\sqrt3 BM. Correct. B: Ni2+\mathrm{Ni^{2+}} is d8d^8; four Cl−\mathrm{Cl^-} ligands give a tetrahedral, high-spin complex with two unpaired electrons, μ=8\mu=\sqrt8 BM. Correct. C: In [Co(en)2Cl2]+[\mathrm{Co(en)_2Cl_2}]^+ the trans isomer is achiral, while the cis isomer is chiral and exists as a pair of enantiomers, giving 1+2=31+2=3 stereoisomers (checked by enumerating all placements of two cis-spanning chelates and two Cl on an octahedron modulo rotations). Correct. D: Co3+\mathrm{Co^{3+}} is d6d^6 and F−\mathrm{F^-} is a weak-field ligand, so [CoF6]3−[\mathrm{CoF_6}]^{3-} is high spin t2g4eg2t_{2g}^4e_g^2 with four unpaired electrons, hence paramagnetic. Incorrect. Answer: A, B, C.
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