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Ch.21 - Transition Elements and Coordination Chemistry
Chapter 21, Problem 126d

Give a valence bond description of the bonding in each of the following complexes. Include orbital diagrams for the free metal ion and the metal ion in the complex. Indicate which hybrid orbitals the metal ion uses for bonding, and specify the number of unpaired electrons.
(d) [MnCl6]32 (high-spin)

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1
Identify the oxidation state of the metal ion in the complex. For [MnCl_6]^{3-}, determine the oxidation state of Mn by considering the charge of the complex and the charge of the ligands.
Determine the electron configuration of the free metal ion. Manganese (Mn) has an atomic number of 25, so its electron configuration is [Ar] 3d^5 4s^2. Adjust this configuration for the oxidation state found in step 1.
Draw the orbital diagram for the free metal ion, showing the distribution of electrons in the 3d, 4s, and 4p orbitals.
Consider the effect of the ligands on the metal ion. Since [MnCl_6]^{3-} is a high-spin complex, the chloride ligands are weak field ligands and do not cause significant pairing of electrons in the d orbitals.
Determine the hybridization of the metal ion in the complex. For an octahedral complex like [MnCl_6]^{3-}, the metal ion typically uses d^2sp^3 hybrid orbitals for bonding. Indicate the number of unpaired electrons based on the high-spin configuration.

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Key Concepts

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

Valence Bond Theory

Valence Bond Theory (VBT) explains how atoms bond by overlapping their atomic orbitals to form covalent bonds. In this theory, the shape and orientation of the orbitals are crucial for understanding the geometry of the resulting molecule. VBT also incorporates the concept of hybridization, where atomic orbitals mix to create new hybrid orbitals that can form stronger bonds.
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Valence Shell Electron Pair Repulsion Theory

Hybridization

Hybridization is the process of combining atomic orbitals to create new hybrid orbitals that are degenerate in energy. In transition metal complexes, the type of hybridization (e.g., sp3, d2sp3) determines the geometry of the complex and the orbitals involved in bonding. For the [MnCl6]3- complex, understanding the hybridization helps identify which orbitals are used for bonding with chloride ligands.
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Hybridization

High-Spin vs. Low-Spin Complexes

High-spin and low-spin complexes refer to the arrangement of electrons in the d-orbitals of transition metals in the presence of ligands. High-spin complexes have unpaired electrons in higher energy orbitals due to weaker field ligands, leading to a larger number of unpaired electrons. In contrast, low-spin complexes have paired electrons in lower energy orbitals due to stronger field ligands. The [MnCl6]3- complex is specified as high-spin, indicating a particular electron configuration that affects its magnetic properties.
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For octahedral complexes, Weak-Field Ligands create High-spin complexes and Strong-Field Ligands create Low-spin complexes.