Question:medium

The correct electronic configuration of central metal ion in ferrocene with \(z\)-axis passing through the centre of two \(\mathrm{C_5H_5^-}\) rings and the metal ion is:

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Rank the d-orbitals by overlap with the Cp ring \(\pi\) system: the in-plane pair is lowest (nonbonding), \(d_{z^2}\) is next, and the tilted pair is highest; fill \(d^6\) from the bottom, fully paired since ferrocene is diamagnetic.
Updated On: Jul 20, 2026
  • \(d_{xy}^2 = d_{x^2-y^2}^2 < d_{z^2}^2 < d_{xz}^0 = d_{yz}^0\)
  • \(d_{xz}^2 = d_{yz}^2 < d_{z^2}^2 < d_{x^2-y^2}^0 = d_{xy}^0\)
  • \(d_{xy}^2 = d_{xz}^2 = d_{yz}^2 < d_{x^2-y^2}^0 = d_{z^2}^0\)
  • \(d_{xy}^2 < d_{xz}^2 = d_{yz}^2 < d_{x^2-y^2}^0 < d_{z^2}^0\)
Show Solution

The Correct Option is A

Solution and Explanation

Step 1: Start from the known physical fact: ferrocene is diamagnetic.
Ferrocene has no unpaired electrons, confirmed by experiment. This rules out any option that leaves electrons unpaired across two different-energy sets, and means all six $d$-electrons of $\mathrm{Fe^{2+}}$ ($d^6$) must sit fully paired.

Step 2: Use the geometry of each orbital relative to the two Cp rings.
Picture the rings as flat pentagons above and below the metal, with the sandwich axis as $z$. $d_{xy}$ and $d_{x^2-y^2}$ lie entirely in the equatorial $xy$ plane, roughly between the ring carbon positions, so they barely interact with the ring $\pi$ clouds: a spectator pair, lowest in energy. $d_{z^2}$ points directly up and down the $z$-axis toward the ring centroids, giving a small $\sigma$-type interaction, a middle-energy orbital. $d_{xz}$ and $d_{yz}$ tilt toward the ring carbons and interact most strongly with the filled ring $\pi$ orbitals, pushing this pair highest.

Step 3: Fill six electrons from the bottom up, respecting degeneracy.
The lowest doubly-degenerate pair ($d_{xy},d_{x^2-y^2}$) takes 4 electrons, the next single orbital ($d_{z^2}$) takes the remaining 2, and the highest doubly-degenerate pair ($d_{xz},d_{yz}$) is left empty. Every electron is paired, consistent with diamagnetism.

Step 4: Write the final configuration and confirm against options.
\[ d_{xy}^2 = d_{x^2-y^2}^2 < d_{z^2}^2 < d_{xz}^0 = d_{yz}^0 \]
Option (B) puts the near-nonbonding pair as highest energy, contradicting the weak-overlap argument. Option (C) removes the distinct level for $d_{z^2}$. Option (D) lists four levels instead of the required 2:1:2 degeneracy pattern. Only (A) survives.

Final Answer:
Option (A) is correct. \[\boxed{d_{xy}^2 = d_{x^2-y^2}^2 < d_{z^2}^2 < d_{xz}^0 = d_{yz}^0}\]
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