Bismuth tris

Chlor-wasserstoffsaure, /. hydrochloric acid, -wismut, n. bismuth (tri)chloride. -zink, n. zinc chloride, -zinn, n. tin chloride. 

Procedure. The cold bismuth nitrate solution, containing 0.1-0.15 g of Bi (Note 1), must be slightly acid with nitric acid (Note 2), and occupy a volume of about 20 mL. Add finely powdered solid potassium iodide, slowly and with stirring, until the supernatant liquid above the black precipitate of bismuth tri-iodide is just coloured yellow (due to K[BiI4]). Dilute to 200mL with boiling water, and boil for a few minutes. The black tri-iodide is converted into... 

Bismuth, tris(dipropyldithiophosphonium)-stereochemistry, 1, 81 Bismuthate, hexabromo-structure, 1,73 Bismuthate, hexachloro-structure, 1, 73 Bismuthate, hexaiodo-structure, 1, 73... 

Ammino-bismuth Iodides.—Bismuth triodide absorbs ammonia gas on heating, forming a red crystalline mass of triammino-bismuth tri-iodide, [Bi(NH3)3]I3.6 From this, water abstracts ammonium iodide without change of colour of the substance. 

Reagent. Dissolve 1 g of bismuth subnitrate in 3 ml of lOM hydrochloric acid with the aid of heat, dilute to 20ml with water, and dissolve in the mixture 1 g of potassium iodide. If black bismuth tri-iodide separates, add 2M hydrochloric acid and more potassium iodide to dissolve it. 

Acetylaminophenylarsine (2-1 parts) is dissolved in 30 parts of methyl alcohol containing hydrogen bromide, and 4 5 parts of bismuth tri-bromide in methyl alcohol added. Addition of ether precipitates a heavy, black powder, decomposed by acids and alkalis. 

Bismuth tri-lu oinide. Dry etlior solution. Triphenylbismuthine. Challenger and Allpress, Trans, Gkem. Roc., 1921, 119, 913. 

Via thermolysis of bismuth sulfinates (method L) Thermolysis of bismuth tris(arenesulfinate), which can be prepared from bismuth acetate and arenesulfinic acid in glacial acetic acid, leads to the formation of triarylbismuthines [72AJC2107]. 

Bismuth tris(4-methylbenzenesulfinate) (ca. 0.1-0.2 g) was heated in a sublimation apparatus at 200°C/10 -10 mmHg. After 5 h, the crude sublimed product was collected and recrystal-... 

Diphenylbismuth acetate (164.7 g, 390 mmol) and sodium pyridine-l-oxide-2-thiolate (59.7 g, 390 mmol, 97.3% active) were stirred in DMF (3900 ml) for 15 min at 32°C, and then heated with stirring at 65°C for 1.25 h. The resulting yellow solution was filtered and the filtrate was mixed with dichloromethane and water (1 1 2). The bottom layer was separated and cooled in an ice bath. Yellow crystals of the crude product were washed successively with ether and water, and then dissolved in warm Al,A -dimethylacetamide (ca. 60°C). When the warm solution was filtered normally, small amounts of a solid were observed and shown to be largely bismuth tris(pyridine-l-oxide-2-thiolate). By adding water, phenylbismuth bis(pyridine-l-oxide-2-thio-late) was precipitated, collected by filtration and washed three times with water and ether. The yield of the product was 42% [72JCS(D)1120]. 

A solution of Ph3Bi (1 g) in dry CHCI3 (6 ml) was added to a solution of chloroacetic acid (0.644 g) in the same solvent (2 ml), and the resulting mixture was stirred for 45 min. The precipitate formed was filtered off and vacuum dried to obtain bismuth tris(chloroacetate) (0.97 g, 90%) [79ZOB1185]. 

A solution of bismuth tris[bis(trimethylsilyl)amide] BifNlSiMetfilt (0.98 g, 1.42 mmol) in light petroleum (10 ml) was added to 2,4,6-trimethylbenzenethiol (1.0 g, 4.25 mmol) in the same solvent (40 ml) at room temperature. The resulting red solution was stirred for 1 h and then the solvent was removed in vacuo. The residue was recrystallized from MeCN-ethyl acetate (3 1 v/ v) to give bismuth tris(2,4,6-trimethylbenzenethiolate) as orange crystals (1.1 g, 86%) [95JCS(D)1649]. 

Ch. 2 Organobismuth(Ill) compounds with Bi-group 15 or 16 element bonds 147 Synthesis of bismuth tris(benzenesulfinate)... 

Solutions of benzenesulfinic acid (ca. 4 mmol) and bismuth acetate (1.0 mmol) in glacial acetic acid (50 and 100 ml, respectively) were mixed and evaporated to dryness under vacuum. The residue was washed with chloroform and dried under a stream of nitrogen to give bismuth tris(benzenesulfinate) in 82% yield [72AJC2107]. 

An excess amount of CO2 was passed to a solution of Bi(NMe2)3 in THF (10 ml), under icecooling. White slurry of fine solid resulted. Replacement of THF by petroleum ether gave a filterable precipitate, which was recrystallized from CHCli-petroleum ether to give bismuth tris(dimethylcarbamate) (4.12 g, 87%) [75JINC(37)2011]. 

When Bi(NMe2)j (1.70 g, 5 mmol) in THF was mixed with a slight excess of CS2 (18 mmol), an exothermic reaction took place to give a yellow slurry. By adding petroleum ether to this slurry, bismuth tris(dimethyldithiocarbamate) was obtained as a yellow solid (2.84 g, 95%) [75JINC(37)2011]. 

THF, a mild exothermic reaction took place with the disappearance of the yellow colour of the bismuth amide. After removal of THF in a rotatory evaporator, the remaining slurry was triturated with petroleum ether to give bismuth tris(lV-phenyl-A, lV -dimethylureide) (2.92 g, 87%) [75JINC(37)2011]. 

Bismuth tris(2-amino-l-cyclopentene-l-dithiocarboxylate) 1 and 2-(ethyla-mino)cyclopentene-l-dithiocar-boxylate 2 are obtained as red crystals by treating BiCl3 or BiOCl with the corresponding dithiocarboxylic acids in EtOH. Compound 1 is insoluble in common organic solvents except for DMF and DMSO, in which it is sparingly soluble. Compound 2 is moderately soluble in common organic solvents [87IC1453]. 

Five examples of bismuth tri(dithiocarbonate)s are known O-methyldithio-carbonate 1, 0-ethyldi-thiocarbonate 2, 0-isopropyldithiocarbonate 3, O-cyclohexyldithio-carbonate 4, and (9-benzyldithiocarbonate 5. All these compounds are prepared by a simple substitution reaction of BiCb with potassium dithiocarbonate [76AJC559, 85ICA(99)177, 92JCSR(22)231]. 

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