Formation of an Unusual <i>Pseudo</i>-Square Planar-Induced Mercury(II) Dimeric Complex

Abstract

Due to the different crystallization methods, two Hg(II) complexes of a 19-membered NO2S2-macrocycle (L) and its oxidized ligand (HLox), exhibiting different stoichiometries, were prepared. First, mercury(II) iodide reacts with L to afford a dinuclear metallacycle complex [Hg2(L)2I4] (1) in which the mercury(II) exists outside the macrocyclic cavity. Meanwhile, the slow diffusion reaction gave an unusual pseudo-square planar-induced mercury(II) complex, which shows three separated parts with the formula [Hg2(HLox)I5]2[HgI2] (2). There are two complex cation units that are exo-coordinated, along with one unit consisting of a metal cluster anion. Surprisingly, L was oxidized in the disulfoxidized form (HLox) in this condition. NMR titration was used to monitor both the structural and binding characteristics of the complex formed between L and mercury(II) iodide in a solution.

Keywords

• thiamacrocycle
• mercury iodide
• dimeric complex
• exocyclic coordination
• sulfoxidation