Synthesis and structure of dithizonato complexes of antimony(III), copper(II) and tin(IV)

Abstract

In view of the important role of dithizone in trace metal analyses, new structural aspects and approaches used to probe metal complexes of dithizone are of interest. Three X-ray diffraction structures are reported, dichloridobis(dithizonato)tin(IV), dichlorido(dithizonato)antimony(III), and bis(dithizonato)copper(II). During synthesis of the tin complex, auto-oxidation of SnIICl2 to SnIV occurred without chloride liberation. The SbIII complex revealed a unique distorted see-saw geometry which is, as for the other complexes, predicted by DFT molecular orbital calculations. The computed products of the lowest energy reactions are in agreement with experimentally obtained reaction products, which, together with molecular orbital renderings serve as a tool toward prediction of modes of coordination in these complexes. The S–M–N bond angle in the five-membered coordination ring shows a linear relationship with the corresponding metal ionic radii.