Chapter 5, Problem 5.1P

Expand the list of orbitais considered in Figures 5.2 and 5.3 by using all three p orbitals of atom A and all five d orbitals of atom B. Which of these have the necessary match ofsymmetry for bonding and antibondingorbitals? These combinations are rarely seen in simplemolecules but can be important in transition metal complexes.

Interpretation Introduction

Interpretation: The list of orbitals should be expanded using all three p-orbitals of atom A and all five d-orbitals of atom B and the orbitals should be selected which has necessary match of symmetry for bonding and antibonding orbitals.

Concept Introduction: Three conditions are considered for overlapping which leads to bonding.

1. The orbital’s symmetry must be such that regions with the same sign of ψ overlap.
2. The energies of atomic orbital must be comparable.
3. In order to provide good overlap, the distance between the atoms should be short enough but not so short as the repulsion of other electrons or nuclei occur.

Answer to Problem 5.1P

Bonding interactions -

  $\begin{array}{l}{\text{p}}_z{\text{ and d}}_{z^2}\\ {\text{p}}_y{\text{ and d}}_{yz}\\ {\text{P}}_x{\text{ and d}}_{xz}\end{array}$

P orbitals and ${\text{d}}_{x^2-y^2}{\text{ and d}}_{xy}$ form anti-bonding interactions.

Explanation of Solution

The shapes of p orbitals are as follows:

  

The shapes of d orbitals are as follows:

  

There are three possible bonding interactions. They are,

  $\begin{array}{l}{\text{p}}_z{\text{ and d}}_{z^2}\\ {\text{p}}_y{\text{ and d}}_{yz}\\ {\text{P}}_x{\text{ and d}}_{xz}\end{array}$

P orbitals and ${\text{d}}_{x^2-y^2}{\text{ and d}}_{xy}$ form anti-bonding interactions.