Synthesis and characterization of methylbismuth(III) complexes containing dithio ligands: 2. Crystal and molecular structure of [MeBiCl(S2CNEt2)] and transformation of some [MeBi(S2CNR2′)2] to Bi2S3

Reactions of methylbismuth(III) dichloride with sodium salts of dithiocarbamates have been carried out in 1:1 and 1:2 stoichiometric ratios in anhydrous benzene to yield products of the types [MeBiCl(S2CNR2)] [where R = Me (1), Et (2) and iPr (3)] and [MeBi(S2CNR2′)2].These complexes were characterized by elemental analyses and by FT-IR and NMR (1H and 13C) spectra. The X-ray structure of [MeBiCl(S2CNEt2)] (2), indicates the presence of unique Bi⋯Cl⋯Bi secondary bonds resulting in a distorted square pyramidal environment around the central bismuth(III) atom. TGA of (6) shows a single step break down of the complex to Bi2S3 at 262.8 °C. Transformations of (6) and (8) to pure Bi2S3 have been carried out successfully in refluxing xylene (142 °C) as revealed by XRD and SEM studies.

Graphical abstractMethylbismuth(III) complexes containing dithio ligands of the types [MeBiCl(S2CNR2)] and [MeBi(S2CNR2′)2] have been synthesized and characterized. Crystal structure of [MeBiCl(S2CNEt2)] indicates the presence of unique Bi⋯Cl⋯Bi secondary bonds resulting in a distorted square pyramidal environment around the central bismuth(III) atom. TGA, XRD and SEM studies indicate low temperature transformation of some [MeBi(S2CNR2′)2] to pure Bi2S3.Figure optionsDownload full-size imageDownload as PowerPoint slide