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Q.Predict the number of unpaired electrons in the square planar [Pt(CN)4]2−[Pt(CN)_4]^{2-} ion.

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The key is to determine the oxidation state of Pt, then its d-electron count, and finally the crystal field splitting in a square planar geometry. For [Pt(CN)4]2−[Pt(CN)_4]^{2-}, Pt is in the +2 state with a d8d^8 configuration, and the strong-field CN⁻ ligands cause pairing of all electrons, giving zero unpaired electrons.

Why This Approach Works

Magnetic moment tells us about unpaired electrons. To predict them, we need two things: the number of d-electrons on the central metal ion, and how those electrons arrange themselves under the influence of the ligands.

Square planar geometry is a special case. It arises most commonly for d8d^8 metal ions with strong-field ligands — think Ni²⁺, Pd²⁺, Pt²⁺. The crystal field splitting in a square planar complex is essentially an extreme version of octahedral splitting where two trans ligands are removed, causing one set of d-orbitals to rise dramatically in energy. The result is a large energy gap between the lower and upper d-orbitals, forcing electrons to pair up.

CN⁻ is a strong-field ligand (high up in the spectrochemical series). So we expect maximum pairing.

Let’s walk through it step by step.


  1. Find the oxidation state of platinum. The complex ion is [Pt(CN)4]2−[Pt(CN)_4]^{2-}. Each CN⁻ ligand carries a –1 charge. Let the oxidation state of Pt be xx.

x+4(−1)=−2⇒x−4=−2⇒x=+2x + 4(-1) = -2 \quad \Rightarrow \quad x - 4 = -2 \quad \Rightarrow \quad x = +2

So platinum is in the +2 oxidation state.

  1. Determine the d-electron count for Pt(II).

    Platinum (Pt) has atomic number 78. Its ground-state electron configuration is [Xe] 4f14 5d9 6s1[Xe]\,4f^{14}\,5d^9\,6s^1.

    When Pt loses two electrons to become Pt²⁺, it loses the 6s electron first, then one 5d electron.

    So Pt²⁺ has the configuration [Xe] 4f14 5d8[Xe]\,4f^{14}\,5d^8.

    That’s a d8d^8 system.

  2. Recall the crystal field splitting pattern for square planar geometry.

    In a square planar complex, the d-orbital energies (from lowest to highest) are:

    • dxz,dyzd_{xz}, d_{yz} (degenerate, lowest)
    • dz2d_{z^2} (slightly higher)
    • dxyd_{xy} (higher still)
    • dx2−y2d_{x^2-y^2} (highest, by a large margin)

    The energy gap between the dxyd_{xy} and dx2−y2d_{x^2-y^2} orbitals is very large — comparable to or larger than the pairing energy for a d8d^8 ion with strong-field ligands.

    For square planar d8d^8 with strong-field ligands, the splitting is so large that all eight electrons occupy the four lower orbitals, leaving the dx2−y2d_{x^2-y^2} orbital empty.

  3. Fill the electrons according to Hund’s rule and the Aufbau principle. …

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