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Q.Justify with reasons:

(i) [NiCl4]2−[NiCl_4]^{2-} is paramagnetic while [Ni(CO)4][Ni(CO)_4] is diamagnetic, although both are tetrahedral.
(ii) [Fe(H2O)6]3+[Fe(H_2O)_6]^{3+} is stronger paramagnetic while [Fe(CN)6]3−[Fe(CN)_6]^{3-} is weaker paramagnetic.
Uttar Pradesh UpmspUP Board (UPMSP) Intermediate 2023Subjective· 2mImportance★★★★★
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Magnetic behaviour depends on the number of unpaired dd electrons, set by the ligand field strength. Weak ligands leave more unpaired electrons (more paramagnetic); strong ligands force pairing (fewer unpaired, less/no paramagnetism).

(i) [NiCl4]2−[NiCl_4]^{2-} vs [Ni(CO)4][Ni(CO)_4] — both tetrahedral:

  • [NiCl4]2−[NiCl_4]^{2-}: Ni is +2+2 ⇒3d8\Rightarrow 3d^8. Cl−Cl^- is a weak-field ligand and does not force pairing; hybridisation is sp3sp^3. The 3d83d^8 configuration keeps two unpaired electrons ⇒\Rightarrow paramagnetic.
  • [Ni(CO)4][Ni(CO)_4]: Ni is 00 ⇒3d84s2\Rightarrow 3d^8 4s^2. CO is a strong-field ligand; the 4s4s electrons pair into the 3d3d orbitals giving 3d103d^{10}, and the empty 4s,4p4s,4p form sp3sp^3 hybrids. With 3d103d^{10} all electrons are paired ⇒\Rightarrow diamagnetic.

(ii) [Fe(H2O)6]3+[Fe(H_2O)_6]^{3+} vs [Fe(CN)6]3−[Fe(CN)_6]^{3-}: Both have Fe3+=3d5Fe^{3+} = 3d^5.

  • H2OH_2O is a weak-field ligand ⇒\Rightarrow high-spin, electrons stay unpaired: t2g3eg2t_{2g}^{3}e_{g}^{2}, 5 unpaired electrons ⇒\Rightarrow strongly paramagnetic. …

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