Chapter 22, Problem 22.72QP

(a)

Interpretation Introduction

Interpretation: The crystal field splitting of the given structures to be interpreted.

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.

To Identify: The crystal field splitting of the given structures to be interpreted.

Explanation of Solution

Interpret the reason.

Orbital Splitting diagram of linear complex:

In the linear structure, the ligands which are pointing directly towards the z-axis, the ${\text{d}}_{z^2}$ orbital of the metal ion gains highest energy. The ${\text{d}}_{\text{xz}},{\text{d}}_{\text{yz}}$ orbitals are equivalent in energy which lies below, and ${\text{d}}_{{\text{x}}^2{\text{-y}}^2}$ $,{\text{d}}_{\text{xy}}$ both exhibits similar energy gains the least energy in the splitting.

(b)

Interpretation Introduction

Interpretation: The crystal field splitting of the given structures to be interpreted.

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.

To Identify: The crystal field splitting of the given structures to be interpreted.

Explanation of Solution

Interpret the reason.

Orbital Splitting diagram of trigonal complex:

In the trigonal structure, the ligands which are pointing directly towards the x-axis and y-axis, the ${\text{d}}_{{\text{x}}^2{\text{-y}}^2}$ $,{\text{d}}_{\text{xy}}$ orbitals of the metal ion gains highest energy (because the ligands are present in the xy –plane). The ${\text{d}}_{\text{xz}},{\text{d}}_{\text{yz}}$ orbitals are equivalent in energy which lies below, and ${\text{d}}_{z^2}$ orbitals exhibits least energy (because along the z-axis no ligands are present) in the splitting.

(c)

Interpretation Introduction

Interpretation: The crystal field splitting of the given structures to be interpreted.

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.

To Identify: The crystal field splitting of the given structures to be interpreted.

Explanation of Solution

Interpret the reason.

Orbital Splitting diagram of trigonal bipyramidal complex:

In the trigonal bipyramidal structure, the ligands which are pointing directly towards the z-axis, the ${\text{d}}_{z^2}$ orbital of the metal ion gains highest energy. The ${\text{d}}_{{\text{x}}^2{\text{-y}}^2}$ $,{\text{d}}_{\text{xy}}$ orbitals are equivalent in energy which lies below (because the ligands are present in the xy –plane), and ${\text{d}}_{\text{xz}},{\text{d}}_{\text{yz}}$ orbitals exhibits least energy (because along the z-axis two ligands are present but on the xy-plane three ligands are present) in the splitting.