Lone Pair - Unusual Lone Pairs

Unusual Lone Pairs

A stereochemically active lone pair is also expected for divalent lead and tin ions due to their formal electronic configuration of ns2. In the solid state this results in the distorted metal coordination observed in the litharge structure adopted by both PbO and SnO. The formation of these heavy metal ns2 lone pairs which was previously attributed to intra-atomic hybridization of the metal s and p states has recently been shown to have a strong anion dependence. This dependence on the electronic states of the anion can explain why some divalent lead and tin materials such as PbS and SnTe show no stereochemical evidence of the lone pair and adopt the symmetric rocksalt crystal structure.

In molecular systems the lone pair can also result in a distortion in the coordination of ligands around the metal ion. The lead lone pair effect can be observed in supramolecular complexes of Lead(II) nitrate and in 2007 a study linked the lone pair to lead poisoning. Lead ions in the human metabolism replace native metallic ions in several key proteins, for example: zinc cations in the ALAD protein, which is also known as Porphobilinogen synthase. This seems to be the molecular basis of "lead poisoning", or "saturnism" ("plumbism"). Computational experiments reveal that although the coordination number does not change upon substitution in calcium-binding proteins, the introduction of lead distorts the way the ligands organize themselves to accommodate such an emerging lone pair: consequently, these proteins are perturbed. This lone-pair effect becomes dramatic for zinc-binding proteins, such as the above-mentioned porphobilinogen synthase, as the natural substrate cannot bind anymore: in those cases the protein is inhibited.

Group 14 lone pairs manifest themselves in triple bonds as well. The familiar alkynes have bond order 3 with 180° bond angles (A) but going down the row germanium to germanium formal triple bonds have an effective bond order 2 with one lone pair (B) and trans-bent geometries. In lead the bond order is even 1 with lone pairs for each lead atom (C). In the organogermanium compound D, the bond order is also 1 with complexation of the acidic isonitrile groups based on interaction with germaniums empty 4p orbital