Bismuth dichloride

Tris(2,4,6-trimethylphenyl)bismuthine (1 g, 1.8 mmol) dissolved in dry benzene was treated with dry gaseous chlorine until an excess was evident. Partial evaporation of the solvent, followed by addition of methanol, gave tris(2,4,6-trimethylphenyl)bismuth dichloride as a pale green solid (0.85 g, 76%), m.p. 149-150°C [41JA207]. 

Deprotection of tris(methoxymethoxyphenyl)bismuth dichlorides affords the corresponding tris(hydroxyphenyl)bismuth dichlorides, the para-isomer of which is acetylated by acetic anhydride/pyridine at the hydroxyl group to yield tris(4-acetoxyphenyl)bismuth dichloride [98JCS(P1)2511]. 

Metathesis of triarylbismuth dichloride with a variety of metal salts such as fluoride, azide, cyanide, carboxylates and sulfonates has been used frequently for the synthesis of triarylbismuth(V) compounds of the type Ar Bi Y 2, where Y is the corresponding anionic group (Section 3.1.1). The reaction of triphenyl-bismuth dichloride with mercuric chloride in an alkaline medium leads to triphenylbismuthine, while treatment of triphenylbismuth dicyanide with mercuric oxide results in the formation of triphenylbismuthine oxide (Section... 

In some limited solvent systems, a metathetical reaction between triphenyl-bismuth dichloride and silver perchlorate results in the formation of oxybis-(triphenylbismuth) diperchlorate [72JOM(36)323]. This type of compound is only obtained when a mixture of water-benzene is used as the reaction medium. When the same reaction is carried out in absolute ethanol or in pure acetone, tetraphenylbismuthonium perchlorate and acetonyltriphenylbismuthonium perchlorate are obtained as the respective product (Section 3.3.1). 

Synthesis of oxybis[tris(4-A, A -dimethylaminophenyl)bismuth] dichloride... 

Tris(4-A, Af-dimethylaminophenyl)bismuth dichloride (0.100 g, 0.156 mmol) was dissolved in reagent grade dichloromethane (20 ml) in the presence of 1.5 equiv. of NaOH (5 mg). The solution was stirred for 3 h and filtered. The filtrate was concentrated to about 4 ml and kept at 0°C. After a few days, oxybis[tris(4-N,N-dimethylaminophenyl)bismuth] dichloride was obtained as yellow crystals in 35% yield (m.p. 159°C, decomp.) [960M5613]. 

Silver cyanate (0.3 g, 2 mmol) was added to an acetone (50 ml) solution of oxybis(triphenyl-bismuth) dichloride (970 mg, 1 mmol) and the mixture was stirred for 5 h at around 5°C. It was then filtered and the filtrate was concentrated under vacuum. By adding water to the solution, oxybis(triphenylbismuth) dicyanate was obtained as a fine white powder. The compound was filtered and crystallized twice from dry acetone and diethyl ether Yield 40%, m.p. 139°C (decomp.) [72JOM(36)323]. 

To a mixture of tris(2-methylphenyl)bismuth dichloride (2.21 g, 4.15 mmol), trifluoroacetamide (458 mg, 4.05 mmol) and dichloromethane (80 ml) was added potassium fert-butoxide (998 mg, 8.91 mmol) at —50°C. The resulting mixture was allowed to warm gradually to 10°C with vigorous stirring. The insoluble solid was filtered through Celite and the filtrate was concentrated under reduced pressure to leave an oily residue, which was crystallized from dichloro-methane-hexane to give tris(2-methylphenyl)bismuthine A trifluoroacetylimide as a pale yellow solid (2.205 g, 90%), m.p. 108-116°C (decomp.) [99OM2580]. 

When a pentavalent bismuth dichloride 54 is refluxed in dichloromethane, reductive elimination takes place smoothly to give chlorobismuthine (52e) quantitatively together with 4-chlorotoluene. This process is considered to be facilitated by the transannular effect. 

C2 H2 BiCl2 Dichlorotris(4-methylphenyl)bismuth (tris(4-methylphenyl)-bismuth dichloride) 6.6-49 o n 3... 

Oxybis[ tris[4-(A, /7-dimethylamino)phenyl]bismuth dichloride 280 Phenylbismuth bis(dimethyldithiocarbamate) 122 Phenylbismuth bis(pyridine-l-oxide-2-thiolate) 123 Phenylbismuth diethoxide 121 Phenylbismuth ethanedithiolate 353 Phenylbismuth oxalate 122, 352... 

A chain-like polymeric self-organization, 194, is observed in Tr-cyclopentadienyl bismuth dichloride, C5H5BiCl2. Pseudorotational disorder results in a mixture of and bonding of the C5H5 ring to the metal atom. The chains are formed by double chloride bridging and the bismuth-chlorine interatomic distances differ [455]. 

Acid Halogenides. For acid halogenides the name is formed from the corresponding acid radical if this has a special name (Sec. 3.1.2.10) for example, NOCl, nitrosyl chloride. In other cases these compounds are named as halogenide oxides with the ligands listed alphabetically for example, BiClO, bismuth chloride oxide VCI2O, vanadium(lV) dichloride oxide. 

Barton and co workers have explored the aryladon of various nucleophiles inclndmg nitroalkanes using bismuth reagents Reacdon of 2-nitropropane v/ith triphenylbismnth carbonate gives 2-nitro-2-phenylpropane in 80% yield Recently, this aryladon has been used for the synthesis of unusual amino acids Aryladon of ct-nitro esters v/ith triphenylbismnth dichloride followed by redncdon gives unique ct-amino acids fEq 5 68 ... 

The anodic dissolution of magnesium. Mg, has been reported as possible in the basic or buffered ionic liquids that consist of EMI+ and DMPI [20]. However, the deposition of Mg is impossible due to the instability of metallic Mg against these organic cations, whereas the formation of Al-Mg alloys containing Mg up to 2.2 at% has been observed in the acidic EMICI-AICI3 ionic liquid [21]. Calcium and strontium dichlorides, CaCla and SrCla, are soluble in an acidic EMICI-AICI3 ionic liquid and the co-deposition of calcium and strontium with bismuth and copper has been examined in the acidic ionic liquid [22]. 

Organobismuth(III) halides may be prepared by elimination of aryl halide from triarylbismuth(V) dichlorides or dibromides upon heating (equation 4). Presumably, a bis-muth(V) compound is the intermediate when triarylbismuth compounds are treated with iodine or when trialkylbis-muth complexes are treated with chlorine, bromine, or iodine, but the intermediates have not been isolated and organobismuth halides are obtained directly (equation 5). The tris(trifluoromethyl)bismuth behaves like the trialkyl compounds without the observation of a bismuth(V) intermediate. ... 

The body shows decomposition if heated above 270° C. and burns in air with a reddish flame and the separation of lead oxide. It is moderately soluble in chloroform, benzene, or carbon bisulphide when hot, and difficultly soluble in alcohol, ether, ligroin, or acetic acid. If heated in a sealed tube with hydrochloric acid decomposition occurs, lead tetrachloride and benzene being produced. By the action of halogens or concentrated nitric acid two phenyl groups are split off, and a lead diphenyl dihalide or dinitrate formed. A similar action takes place with iodic acid, formic, acetic, trichloracetic, propionic, valeric, and p-nitrobenzoic acids. With metallic chlorides the following derivatives are formed arsenic trichloride — lead diphenyl dichloride and diphenyl arsenious chloride antimony trichloride — lead diphenyl dichloride and diphenylstibine chloride antimony penta-chloride — lead diphenyl dichloride and diphenylstibine trichloride bismuth tribromide —> lead diphenyl dichloride and diphenylchloro-bismuthine thallie chloride —> lead diphenyl dichloride and thallium diphenyl chloride tellurium tetrachloride —> lead diphenyl dichloride and tellurium diphenyl dichloride. 

---