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Q.(a) [Co(NH3)6]3+[Co(NH_3)_6]^{3+} is diamagnetic whereas [CoF6]3−[CoF_6]^{3-} is paramagnetic. Justify the statement. [Atomic number of Co = 27]

(b) Write the electronic configuration for d4d^4 ion if Δ0>P\Delta_0 > P on the basis of crystal field theory.
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The difference in magnetic behaviour arises because NH3NH_3 is a strong field ligand causing large splitting (Δ0>P\Delta_0 > P) leading to pairing, while F−F^- is a weak field ligand with small splitting (Δ0<P\Delta_0 < P) favouring high-spin configuration. For a d4d^4 ion with Δ0>P\Delta_0 > P, the configuration is t2g4eg0t_{2g}^4 e_g^0 (low-spin).

The Core Idea: Crystal Field Splitting and the "Pairing Energy" Battle

The magnetic behaviour of a coordination complex — whether it is diamagnetic (all electrons paired) or paramagnetic (some unpaired electrons) — depends entirely on how the dd-electrons of the central metal ion arrange themselves in the presence of ligands. This is governed by Crystal Field Theory (CFT).

When ligands approach a metal ion, the five degenerate dd-orbitals split into two sets: the lower-energy t2gt_{2g} set (dxy,dyz,dzxd_{xy}, d_{yz}, d_{zx}) and the higher-energy ege_g set (dx2−y2,dz2d_{x^2-y^2}, d_{z^2}). The energy gap between them is called Δ0\Delta_0 (crystal field splitting energy for octahedral complexes).

Now, here's the crucial question: when you place a d4d^4, d5d^5, d6d^6, or d7d^7 electron into this split set, do the electrons pair up in the lower t2gt_{2g} orbitals, or do they occupy the higher ege_g orbitals first? The answer depends on a tug-of-war between two energies:

  1. Δ0\Delta_0 — the energy cost to promote an electron from t2gt_{2g} to ege_g.
  2. PP (Pairing Energy) — the energy cost to force two electrons into the same orbital (due to electron-electron repulsion).

The rule is simple:

  • If Δ0>P\Delta_0 > P: Electrons prefer to pair in t2gt_{2g} → Low-spin complex (more paired, less paramagnetic).
  • If Δ0<P\Delta_0 < P: Electrons prefer to occupy ege_g orbitals singly first → High-spin complex (more unpaired, more paramagnetic).

The value of Δ0\Delta_0 is determined by the nature of the ligand. Ligands that cause a large splitting are called strong field ligands (e.g., NH3NH_3, CN−CN^-, COCO). Ligands that cause a small splitting are called weak field ligands (e.g., F−F^-, Cl−Cl^-, H2OH_2O).


Part (a): Comparing [Co(NH3)6]3+[Co(NH_3)_6]^{3+} and [CoF6]3−[CoF_6]^{3-}

Let's apply this to the two complexes.

Step 1: Determine the oxidation state and dd-electron count of Cobalt.

Atomic number of Co = 27. Ground state configuration: [Ar]3d74s2[Ar] 3d^7 4s^2.

  • For [Co(NH3)6]3+[Co(NH_3)_6]^{3+}: NH3NH_3 is neutral. So, x+6(0)=+3  ⟹  x=+3x + 6(0) = +3 \implies x = +3. Co is in +3 state.
    • Co3+Co^{3+}: Remove 3 electrons (2 from 4s, 1 from 3d). Configuration: 3d63d^6.
  • For [CoF6]3−[CoF_6]^{3-}: F−F^- has charge -1. So, x+6(−1)=−3  ⟹  x=+3x + 6(-1) = -3 \implies x = +3. Co is also in +3 state.
    • Co3+Co^{3+}: Again, 3d63d^6.

Both complexes have a d6d^6 metal ion. The difference lies entirely in the ligand.

Step 2: Identify the ligand field strength and predict the spin state.

  • [Co(NH3)6]3+[Co(NH_3)_6]^{3+}: NH3NH_3 is a strong field ligand. It causes a large Δ0\Delta_0. For Co3+Co^{3+}, Δ0\Delta_0 is so large that Δ0>P\Delta_0 > P.

    • Consequence: The six dd-electrons will all pair up in the three t2gt_{2g} orbitals before any electron goes to ege_g.
    • Configuration: t2g6eg0t_{2g}^6 e_g^0.
    • Magnetic Behaviour: All electrons are paired. The complex has zero unpaired electrons. Therefore, it is diamagnetic (weakly repelled by a magnetic field).
  • [CoF6]3−[CoF_6]^{3-}: F−F^- is a weak field ligand. It causes a small Δ0\Delta_0. For Co3+Co^{3+}, Δ0\Delta_0 is small enough that Δ0<P\Delta_0 < P.

    • Consequence: The electrons will follow Hund's rule of maximum multiplicity. They will first occupy all five dd-orbitals singly before pairing.
    • Configuration: Following the aufbau principle for the split orbitals: t2g4eg2t_{2g}^4 e_g^2. (First, 3 electrons go into t2gt_{2g} singly, the 4th pairs in t2gt_{2g}, and the 5th and 6th go singly into ege_g).
    • Magnetic Behaviour: There are 4 unpaired electrons (2 in t2gt_{2g} and 2 in ege_g). Therefore, it is paramagnetic (strongly attracted by a magnetic field). …

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