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

Abstract

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(S 2 CNR 2 )] [where R = Me (1), Et (2) and i Pr (3)] and,andThese complexes were characterized by elemental analyses and by FT-IR and NMR ( 1 H and 13 C) spectra. The X-ray structure of [MeBiCl(S 2 CNEt 2 )] (2), indicates the presence of unique BiÁ Á ÁClÁ Á ÁBi 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 Bi 2 S 3 at 262.8°C. Transformations of (6) and (8) to pure Bi 2 S 3 have been carried out successfully in refluxing xylene (142°C) as revealed by XRD and SEM studies.

Synthesis of Bi2S3 Nanostructures from Bismuth(III) Thiourea and Thiosemicarbazide Complexes

“…6, [15][16][17][18][19][20][21][22][23][24][25][26][27][28] It is almost certain that the conversion to nanoparticles in these systems involves prior coordination of the S-based ligand, and decomposition of preassembled sulfur-containing bismuth(III) complexes may afford some advantages in control over the shape and size of the particles formed. [15][16][17][18][19][20][21] Bismuth(III) routinely adopts coordination numbers higher than six and stable aminopolycarboxylate (APC) and polyaminopolycarboxylate (PAPC) complexes that also contain sulfur-based ligands have been reported. 29 Tian et al 15 have recently reported a colloidal solution method to prepare Bi 2 S 3 nanorods and dandelion-like nanostructures from Bi(SCOPh) 3 in binary surfactant systems at 150 °C.…”

“…Uniform Bi 2 S 3 flowers with a size of 3−5 μm composed of nanowires with a diameter of 80 nm can be prepared from BiCl 3 and acetothioamide in the presence of the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate . Other strategies to produce Bi 2 S 3 nanostructures have been described. ,− …”

“…It is almost certain that the conversion to nanoparticles in these systems involves prior coordination of the S-based ligand, and decomposition of preassembled sulfur-containing bismuth(III) complexes may afford some advantages in control over the shape and size of the particles formed. − Bismuth(III) routinely adopts coordination numbers higher than six and stable aminopolycarboxylate (APC) and polyaminopolycarboxylate (PAPC) complexes that also contain sulfur-based ligands have been reported . Tian et al have recently reported a colloidal solution method to prepare Bi 2 S 3 nanorods and dandelion-like nanostructures from Bi(SCOPh) 3 in binary surfactant systems at 150 °C.…”

Routes to Nanostructured Inorganic Materials with Potential for Solar Energy Applications

“…Bismuth complexes used for the synthesis of Bi 2 S 3 nanostructures include bismuth(III) thioacetates [Bi(SCOPh) 3 ], pyridine and 1,10-phenanthroline adducts of bismuth(III) dithioxanthate complexes [Bi(S 2 COCH(CH 3 )CH 2 CH 3 ) 3 ], bismuth(III) di- n -octyl-dithiophosphate [Bi(S 2 P(OC 8 H 17 ) 2 ) 3 ], , bismuth(III) diethyldithiocarbamate complexes, − bismuth(III) thiourea [Bi 6 (pydc) 8 (Hpydc) 2 (tu) 8 ], and bismuth(III) thiocarbazide {[Bi 2 (pydc) 3 (tsc)(H 2 O) 2 ]·H 2 O} ∞ complexes . Most of these single source precursors produced nanorods or nanotubes with various lengths and diameters.…”

Synthetic, spectral as well as in vitro antimicrobial studies on some bismuth(III) bis(N,N‐dialkyldithiocarbamato) alkylenedithiophosphates

“…Dithiolato moieties like dithiocarbamates1–6 and alkylene‐ dithiophosphates7–11 are versatile ligands and display a broad variety of coordination patterns, leading to a great diversity of molecular and supramolecular structures. With regards to structural studies, these ligands often display bidentate coordination patterns, which may be isobidentate (symmetrical) or anisobidentate (unsymmetrical) both in chelating and bridging situations.…”