Chapter 23, Problem 23.91P

(a)

Interpretation Introduction

Interpretation:

The orbital splitting diagram given ${\left[Fe{(C_2{O}_4)}_3\right]}^3{}^{-}$ complex has to be drawn using the spectrochemical series.

Concept introduction:

Spectrochemical series: The list of ligands arranged in an ascending order of $\text{(Δ)}$ (the splitting of d-orbitals in presence of various ligands).

$\begin{array}{l}\stackrel{{}^{{\text{I}}^{\text{-}}\text{<}{\text{Br}}^{\text{-}}\text{<}{\text{SCN}}^{\text{-}}\text{<}{\text{Cl}}^{\text{-}}\text{<}{\text{S}}^{\text{2-}}\text{<}{\text{F}}^{\text{-}}\text{<}{\text{OH}}^{\text{-}}\text{<}{\text{O}}^{\text{2-}}\text{<}{\text{H}}_{\text{2}}\text{O}\text{<}{\text{NCS}}^{\text{-}}\text{<}{\text{edta}}^{\text{4-}}\text{<}{\text{NH}}_{\text{3}}\text{< en}\text{<}{\text{NO}}^{\text{2-}}\text{<}{\text{CN}}^{\text{-}}\text{<}\text{CO}}}{\to }\\ {}_{{}^{{}^{\begin{array}{l}\text{weak-field}\text{increasing(Δ)}\text{strong-field}\\ \text{ligands}\text{ligands}\end{array}}}}\end{array}$

Crystal field splitting: The energy gap between the splitting of d-orbitals of the metal ion in presence of ligands is known as the crystal field splitting $\text{(Δ)}$.  The magnitude of $\text{(Δ)}$ is depends on the nature of metal ions and the ligands.

In an octahedral complex, the six ligands approach the central metal atom lying at the symmetry along the Cartesian axes.  The orbitals lying along axes $d_{z^2}and{d}_{z^2-y^2}$ get repelled more strongly by the negative ligands and are raised in energy relative to the average energy in between the axes $d_{xy},d_{xz}and{d}_{zy}$

Splitting of five d-orbitals in an octahedral crystals field is as follows:

Figure 1

(b)

Interpretation Introduction

Interpretation:

The orbital splitting diagram given ${\left[Co{(CN)}_6\right]}^{4-}$ complex has to be drawn using the spectrochemical series.

Concept introduction:

Spectrochemical series: The list of ligands arranged in an ascending order of $\text{(Δ)}$ (the splitting of d-orbitals in presence of various ligands).

$\begin{array}{l}\stackrel{{}^{{\text{I}}^{\text{-}}\text{<}{\text{Br}}^{\text{-}}\text{<}{\text{SCN}}^{\text{-}}\text{<}{\text{Cl}}^{\text{-}}\text{<}{\text{S}}^{\text{2-}}\text{<}{\text{F}}^{\text{-}}\text{<}{\text{OH}}^{\text{-}}\text{<}{\text{O}}^{\text{2-}}\text{<}{\text{H}}_{\text{2}}\text{O}\text{<}{\text{NCS}}^{\text{-}}\text{<}{\text{edta}}^{\text{4-}}\text{<}{\text{NH}}_{\text{3}}\text{< en}\text{<}{\text{NO}}^{\text{2-}}\text{<}{\text{CN}}^{\text{-}}\text{<}\text{CO}}}{\to }\\ {}_{{}^{{}^{\begin{array}{l}\text{weak-field}\text{increasing(Δ)}\text{strong-field}\\ \text{ligands}\text{ligands}\end{array}}}}\end{array}$

Crystal field splitting: The energy gap between the splitting of d-orbitals of the metal ion in presence of ligands is known as the crystal field splitting $\text{(Δ)}$.  The magnitude of $\text{(Δ)}$ is depends on the nature of metal ions and the ligands.

In an octahedral complex, the six ligands approach the central metal atom lying at the symmetry along the Cartesian axes.  The orbitals lying along axes $d_{z^2}and{d}_{z^2-y^2}$ get repelled more strongly by the negative ligands and are raised in energy relative to the average energy in between the axes $d_{xy},d_{xz}and{d}_{zy}$

Splitting of five d-orbitals in an octahedral crystals field is as follows:

Figure 1

(c)

Interpretation Introduction

Interpretation:

The orbital splitting diagram given ${\left[Mn{(Cl)}_6\right]}^4{}^{-}$ complex has to be drawn using the spectrochemical series.

Concept introduction:

Spectrochemical series: The list of ligands arranged in an ascending order of $\text{(Δ)}$ (the splitting of d-orbitals in presence of various ligands).

$\begin{array}{l}\stackrel{{}^{{\text{I}}^{\text{-}}\text{<}{\text{Br}}^{\text{-}}\text{<}{\text{SCN}}^{\text{-}}\text{<}{\text{Cl}}^{\text{-}}\text{<}{\text{S}}^{\text{2-}}\text{<}{\text{F}}^{\text{-}}\text{<}{\text{OH}}^{\text{-}}\text{<}{\text{O}}^{\text{2-}}\text{<}{\text{H}}_{\text{2}}\text{O}\text{<}{\text{NCS}}^{\text{-}}\text{<}{\text{edta}}^{\text{4-}}\text{<}{\text{NH}}_{\text{3}}\text{< en}\text{<}{\text{NO}}^{\text{2-}}\text{<}{\text{CN}}^{\text{-}}\text{<}\text{CO}}}{\to }\\ {}_{{}^{{}^{\begin{array}{l}\text{weak-field}\text{increasing(Δ)}\text{strong-field}\\ \text{ligands}\text{ligands}\end{array}}}}\end{array}$

Crystal field splitting: The energy gap between the splitting of d-orbitals of the metal ion in presence of ligands is known as the crystal field splitting $\text{(Δ)}$.  The magnitude of $\text{(Δ)}$ is depends on the nature of metal ions and the ligands.

Splitting of five d-orbitals in an octahedral crystals field is as follows:

Figure 1