Accommodation of the irregular coordination geometry of lead(II) by a square planar N2S2 ligand and its preference for zinc(II).

Abstract

The N2S2 ligand, bis-mercaptoethanediazacyclooctane, coordinates to Pb(II) largely through sulfur donors, enlisting a second unit to fulfill an irregular, hemispherical N2S3 coordination environment in which a void suggests the location of a stereochemically active lone pair on Pb(II). That the highly exposed lead is vulnerable to metal ion displacement is demonstrated on reaction with zinc which results in a regular square pyramidal coordination about zinc within a [N2S2Zn]2 dimer. Analysis of the two dimeric structures finds different connectivities of the monomeric subunits account for the stability of the zinc structure over that of the lead.