Inert Pair Effect - Steric Activity of The Lone Pair

Steric Activity of The Lone Pair

The chemical inertness of the s electrons in the lower oxidation state is not always married to steric inertness, (where steric inertness means that the presence of the s electron lone pair has little or no influence on the geometry of molecule or crystal). A simple example of steric activity is that of SnCl₂ which is bent in accordance with VSEPR. Some examples where the lone pair appears to be inactive are bismuth(III) iodide, BiI₃, and the BiI3−
6 anion. In both of these the central Bi atom is octahedrally coordinated with little or no distortion, in contravention to VSEPR theory. The steric activity of the lone pair has long been assumed to be due to the orbital having some p character, i.e. the orbital is not spherically symmetric. More recent theoretical work shows that this is not always necessarily the case. For example the litharge structure of PbO contrasts to the more symmetric and simpler rock salt structure of PbS and this has been explained in terms of PbII − anion interactions in PbO leading to an asymmetry in electron density. Similar interactions do not occur in PbS. Another example are some thallium(I) salts where the asymmetry has been ascribed to s electrons on Tl interacting with antibonding orbitals.