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Ch.21 - Transition Elements and Coordination Chemistry
Chapter 21, Problem 21.116

Although Cl- is a weak-field ligand and CN- is a strong field ligand, [CrCl6]3- and [Cr(CN)6]3- exhibit approximately the same amount of paramagnetism. Explain.

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Key Concepts

Here are the essential concepts you must grasp in order to answer the question correctly.

Ligand Field Theory

Ligand Field Theory explains how the presence of ligands around a central metal ion affects its electronic structure and the energy levels of its d-orbitals. Strong-field ligands, like CN<sup>-</sup>, cause a larger splitting of d-orbitals compared to weak-field ligands, like Cl<sup>-</sup>. This theory helps in understanding the magnetic properties of coordination complexes based on the arrangement and strength of the ligands.
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Strong-Field Ligands result in a large Δ and Weak-Field Ligands result in a small Δ.

Paramagnetism

Paramagnetism is a form of magnetism that occurs in materials with unpaired electrons. In coordination complexes, the number of unpaired electrons determines the degree of paramagnetism. Both [CrCl<sub>6</sub>]<sup>3-</sup> and [Cr(CN)<sub>6</sub>]<sup>3-</sup> can exhibit similar levels of paramagnetism if they have the same number of unpaired electrons, despite the differences in ligand strength.
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Crystal Field Splitting

Crystal Field Splitting refers to the energy difference between the split d-orbitals in a transition metal complex due to the presence of ligands. In octahedral complexes, the d-orbitals split into two sets: t<sub>2g</sub> and e<sub>g</sub>. The extent of this splitting influences the electron configuration and, consequently, the magnetic properties of the complex, which can lead to similar paramagnetic behavior in complexes with different ligands.
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The crystal field splitting pattern for octahedral complexes has the d orbitals on or along the axes as having the higher energy.