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Question

Consider the figure given below, where M is a metal and L is a monodentate ligand. The $\sigma$-bonding ligand group orbital (LGO) having same symmetry with $d_{z^2}$ orbital of M in the octahedral coordination geometry is

The correct answer is
$\frac{1}{\sqrt{12}}(2\sigma_1 + 2\sigma_2 - \sigma_3 - \sigma_4 - \sigma_5 - \sigma_6)$

To determine the \(\sigma\)-bonding ligand group orbital (LGO) that has the same symmetry as the \(d_{z^2}\) orbital of an octahedral metal complex, we need to consider the symmetry properties of the orbitals involved.

In an octahedral complex, the \(d_{z^2}\) orbital points directly along the z-axis and aligns with the ligands \(\sigma_1\) and \(\sigma_2\) which are positioned along the z-axis. The symmetry of the \(d_{z^2}\) orbital is such that it is symmetric with respect to the z-axis and has no nodal plane perpendicular to the z-axis.

The correct ligand group orbital will have the greatest contribution from the ligands along the z-axis (\(\sigma_1\) and \(\sigma_2\)) and smaller contributions from the other ligands. Therefore, the correct symmetry adapted linear combination (SALC) of the ligand orbitals should reflect these characteristics. Let's analyze the options:

  • \(\frac{1}{\sqrt{12}}(2\sigma_1 + 2\sigma_2 - \sigma_3 - \sigma_4 - \sigma_5 - \sigma_6)\) — This option gives maximum positive weighting to \(\sigma_1\) and \(\sigma_2\), aligning nicely with the character of \(d_{z^2}\).
  • \(\frac{1}{\sqrt{12}}(2\sigma_1 - 2\sigma_2 + \sigma_3 - \sigma_4 + \sigma_5 - \sigma_6)\) — This option gives differing weights to \(\sigma_1\) and \(\sigma_2\), which doesn't fit with the symmetrical nature of \(d_{z^2}\).
  • \(\frac{1}{\sqrt{6}}(\sigma_1 + \sigma_2 - \sigma_3 - \sigma_4 - \sigma_5 - \sigma_6)\) — This has equal weight for \(\sigma_1\) and \(\sigma_2\), but less significant than the positive weights required.
  • \(\frac{1}{\sqrt{6}}(\sigma_1 + \sigma_2 + \sigma_3 + \sigma_4 + \sigma_5 + \sigma_6)\) — This has equal contribution from all ligands, aligning more with the spherically symmetric s-orbital rather than the directional \(d_{z^2}\) orbital.

Thus, the correct answer is:

\(\frac{1}{\sqrt{12}}(2\sigma_1 + 2\sigma_2 - \sigma_3 - \sigma_4 - \sigma_5 - \sigma_6)\)

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Important Questions from Coordination Chemistry

  1. An aqueous solution of $Co(ClO_4)_2 \cdot 6H_2O$ is light pink in colour. Addition of conc. HCl results in an intense blue coloured solution due to the formation of a new species. The new species among the following is


    [Given: Atomic number of Co = 27]

  2. Among the following, the compound with the lowest CO stretching frequency is
  3. The rates of substitution for the following reaction vary with L in the order 

  4. Identify X in the reaction, $[Pt(NH_3)_4]^{2+} + 2 HCl \rightarrow X$
  5. Among the following octahedral complexes, the one that has the highest enthalpy of hydration is
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