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Q.Out of [CoF6]3−[CoF_6]^{3-} and [Co(en)3]3+[Co(en)_3]^{3+}, which one complex is

(i) paramagnetic
(ii) more stable
(iii) inner orbital complex and
(iv) high spin complex (Atomic no. of Co = 27)
CBSECBSE Class XII Board 2019Subjective· 2mImportance★★★★★
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The key is the ligand field strength: F−F^- is a weak field ligand (high spin, outer orbital, paramagnetic), while enen is a strong field ligand (low spin, inner orbital, diamagnetic). Thus [CoF6]3−[CoF_6]^{3-} is paramagnetic and high spin; [Co(en)3]3+[Co(en)_3]^{3+} is more stable and an inner orbital complex.

Let's start with the central idea. The properties of a coordination complex — whether it's paramagnetic or diamagnetic, high spin or low spin, inner or outer orbital — all hinge on one thing: how the ligands split the d-orbitals of the metal ion. This splitting is called Crystal Field Splitting, and its magnitude (Δo\Delta_o for octahedral complexes) depends on the nature of the ligand. Some ligands (like F−F^-) cause a small splitting; others (like enen, ethylenediamine) cause a large splitting. That difference decides everything.

We have cobalt in both complexes. Atomic number 27 means the ground state electron configuration is [Ar]3d74s2[Ar] 3d^7 4s^2. But in a complex, the metal is in an ionic state. Let's find the oxidation state of Co in each.


1. Determine the oxidation state of Co in each complex

  • For [CoF6]3−[CoF_6]^{3-}: Fluoride ion (F−F^-) has a charge of −1-1. Six fluorides give −6-6. The overall charge is −3-3. Let the oxidation state of Co be xx. Then:

x+6(−1)=−3⇒x−6=−3⇒x=+3x + 6(-1) = -3 \quad \Rightarrow \quad x - 6 = -3 \quad \Rightarrow \quad x = +3

So Co is in the +3+3 oxidation state.

  • For [Co(en)3]3+[Co(en)_3]^{3+}: enen (ethylenediamine) is a neutral ligand (no charge). Three neutral ligands contribute 00. The overall charge is +3+3. So:

x+0=+3⇒x=+3x + 0 = +3 \quad \Rightarrow \quad x = +3

Again, Co is in the +3+3 oxidation state.

Both complexes contain Co3+Co^{3+}.


2. Write the d-electron configuration of Co3+Co^{3+}

Cobalt atom: [Ar]3d74s2[Ar] 3d^7 4s^2. Removing three electrons (to get +3+3) means we remove the two 4s electrons and one 3d electron. So Co3+Co^{3+} has 3d63d^6 configuration.

So we have a d6d^6 ion in an octahedral field in both cases. The difference will come from the ligand strength.


3. Recall the Crystal Field Splitting for d6d^6 in octahedral geometry

In an octahedral field, the five d-orbitals split into two sets: the lower-energy t2gt_{2g} (three orbitals) and the higher-energy ege_g (two orbitals). The energy gap is Δo\Delta_o.

For a d6d^6 ion, there are two possible arrangements:

  • High spin (weak field): If Δo\Delta_o is small, electrons prefer to occupy all five orbitals singly before pairing. So the configuration is t2g4eg2t_{2g}^4 e_g^2 — four electrons in t2gt_{2g} (one pair) and two unpaired in ege_g. Total unpaired electrons = 4.
  • Low spin (strong field): If Δo\Delta_o is large, electrons pair up in the lower t2gt_{2g} orbitals before occupying ege_g. So the configuration is t2g6eg0t_{2g}^6 e_g^0 — all six electrons paired in t2gt_{2g}. Total unpaired electrons = 0.

For d6d^6 octahedral:

Weak field (high spin): t2g4eg2t_{2g}^4 e_g^2 — 4 unpaired electrons, paramagnetic.

Strong field (low spin): t2g6eg0t_{2g}^6 e_g^0 — 0 unpaired electrons, diamagnetic.


4. Identify the ligand field strength

  • F−F^- (fluoride) is a weak field ligand. It lies near the end of the spectrochemical series (low Δo\Delta_o). So [CoF6]3−[CoF_6]^{3-} will be high spin.
  • enen (ethylenediamine) is a strong field ligand. It is a chelating ligand (bidentate) and lies high in the spectrochemical series (large Δo\Delta_o). So [Co(en)3]3+[Co(en)_3]^{3+} will be low spin.
Tip

The spectrochemical series (partial): I−<Br−<Cl−<F−<OH−<H2O<NH3<en<NO2−<CN−<COI^- < Br^- < Cl^- < F^- < OH^- < H_2O < NH_3 < en < NO_2^- < CN^- < CO.

F−F^- is to the left (weak), enen is to the right (strong). This is a quick reference for such problems.


5. Answer each part

  1. Paramagnetic complex Paramagnetism arises from unpaired electrons. [CoF6]3−[CoF_6]^{3-} (high spin, t2g4eg2t_{2g}^4 e_g^2) has 4 unpaired electrons — paramagnetic. [Co(en)3]3+[Co(en)_3]^{3+} (low spin, t2g6eg0t_{2g}^6 e_g^0) has all electrons paired — diamagnetic. So the paramagnetic complex is [CoF6]3−[CoF_6]^{3-}.
  2. More stable complex …

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