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Question

Q.(a)

(i) Give reasons : (I) [Ni(CO)4][Ni(CO)_4] is diamagnetic whereas [NiCl4]2−[NiCl_4]^{2-} is paramagnetic. [Atomic number : Ni = 28] (II) CO is a stronger complexing agent than NH3NH_3. (III) The trans isomer of complex [Co(en)2Cl2]+[Co(en)_2Cl_2]^{+} is optically inactive.
(ii) Using Crystal Field theory, write the number of unpaired electrons in octahedral complexes of Fe3+Fe^{3+} in the presence of : (I) Strong field ligand (II) Weak field ligand [Atomic number : Fe = 26]
(OR)
(b)
(i) Name the type of isomerism exhibited by the following compounds. Also draw their corresponding isomers. (I) [Co(NH3)6][Cr(CN)6][Co(NH_3)_6][Cr(CN)_6] (II) [Co(en)3]3+[Co(en)_3]^{3+} (III) [Co(NH3)3(NO2)3][Co(NH_3)_3(NO_2)_3]
(ii) Differentiate between weak field and strong field ligands. How does the strength of the ligand influence the spin of the complex ?
CBSECBSE Class XII Board 2025Subjective· 5mImportance★★★★★
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Part (a): [Ni(CO)4][\text{Ni(CO)}_4] is diamagnetic (3d103d^{10}, strong‑field CO) while [NiCl4]2−[\text{NiCl}_4]^{2-} is paramagnetic (2 unpaired, weak‑field Cl−^-); CO > NH3_3 because of π‑back‑bonding; trans-[Co(en)2Cl2]+[\text{Co(en)}_2\text{Cl}_2]^+ has a plane of symmetry (optically inactive); Fe3+^{3+} gives 1 unpaired e−^- (strong field) or 5 (weak field). Part (b): coordination / optical / (linkage + geometrical) isomerism; strong‑field ligands give low spin, weak‑field give high spin.

Part (a)

(i)(I) Magnetism of the two Ni complexes. Both are tetrahedral, so geometry alone is not the discriminator — the metal's oxidation state and the ligand field are.

  • [Ni(CO)4][\text{Ni(CO)}_4]: Ni(0) is 3d84s23d^8 4s^2. CO is a very strong field ligand; the 4s4s electrons are pushed into the 3d3d set giving 3d103d^{10} — all electrons paired → diamagnetic.
  • [NiCl4]2−[\text{NiCl}_4]^{2-}: Ni(II) is 3d83d^8. Cl−^- is weak field, no pairing occurs; in the tetrahedral field the d8d^8 arrangement leaves two unpaired electrons → paramagnetic.

(i)(II) Why CO > NH3_3. NH3_3 only donates its lone pair (σ‑donor). CO both donates a σ lone pair and accepts metal dd‑electron density into its empty π* orbitals. This synergic σ‑donation/π‑back‑donation strengthens the M–CO bond greatly, so CO is the stronger complexing agent.

(i)(III) Optical inactivity of the trans isomer. Optical activity needs a chiral (non‑superimposable mirror image) molecule. trans-[Co(en)2Cl2]+[\text{Co(en)}_2\text{Cl}_2]^+ has a plane of symmetry through Co and the two axial Cl atoms, so it equals its mirror image → optically inactive. The cis isomer lacks this plane and is optically active.

(ii) CFT for octahedral Fe3+^{3+} (3d53d^5).

  • Strong field ligand (low spin): Δo>P\Delta_o > P, electrons pair in t2gt_{2g} first → t2g5eg0t_{2g}^5 e_g^0 → 1 unpaired electron. …

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