Bismuth III bromide

Bismuth Tribromide. Bismuth(III) bromide is a hygroscopic, golden-yeUow, crystalline soHd made up of pyramidal molecules. X-ray analysis has shown that the three bromines are 0.263 0.002 nm from the bismuth and the Br—Bi—Br angles are 100 4°. More recent nqr experiments indicate that the bromines are not equivalent (20). The soHd has a density of 5.72 g/mL and that of the Hquid is 4.572 g/mL at 271.5°C. 

Bismuth(III) bromide, 4 21 Bismuth bromide sulfide (19 3 27), 4 24 Bismuth bromosulfide, 4 24 Bismuth carboxylates, 4 25 Bismuth chloride, 4 6 Bismuth(III) chloride, 4 19-20 Bismuth chlorosulfide, 4 24 Bismuth compounds, 4 16-43 alloy-like superconducting, 4 18t analysis, 4 17... 

Bismuth(III) Bromide-Catalyzed Synthesis of Substituted Tetrahydroquinoline Derivatives... 

Scheme 5 Bismuth(III) bromide-catalyzed synthesis of substituted tetrahydroquinoline derivatives...

Rogers JL, Emat JJ, Yung H, Mohan RS (2009) Environmentally friendly organic synthesis using bismuth compounds Bismuth(III) bromide catalyzed synthesis of substituted tetrahydroquinoline derivatives. Catal Commun 10 625-626... 

Krabbe SW, Angeles VV, Mohan RS (2010) Bismuth(III) bromide in organic synthesis. A catalytic method for the allylation of tetrahydrofuranyl and tetrahydropyranyl ethers. Tetrahedron Lett 51 5643-5645... 

Ether-bismuth halide adducts also exist. Structural work on bismuth chloride-diethyl ether or THF complexes show that, at low temperature, polymeric chains of 61X3 linked by halide bridges exist and that the bismuth atoms may be coordinated by one or two ether molecules.Bismuth(III) bromide coordinates three THF molecules.These solvent molecules are readily removed under vacuum. The polyethers diglyme and diethylcarbitol give dimeric adducts with BiCR. In the presence of cyclic polyethers, simple coordination, or formation of polyether-coordinated bismuth cations... 

Similar attempted cleavage reactions of the lead-iron derivative with cadmium(II) iodide, copper(II) chloride dihydrate, cobalt(II) chloride hexahydrate, bismuth(III) bromide, and K[Pbl3] failed to give any iron carbonyl derivatives of these metals 198). The black air-sensitive derivative of divalent lead [PbFe(CO)4] has been obtained on treatment of [HFe(CO)4] with basic lead(II) acetate 199). 

The enhancement of SWV net peak current caused by the reactant adsorption on the working electrode surface was utilized for detection of chloride, bromide and iodide induced adsorption of bismuth(III), cadmium(II) and lead(II) ions on mercury electrodes [236-243]. An example is shown in Fig. 3.13. The SWV net peak currents of lead(II) ions in bromide media are enhanced in the range of bromide concentrations in which the nentral complex PbBr2 is formed in the solntion [239]. If the simple electrode reaction is electrochemically reversible, the net peak cnnent is independent of the composition of supporting electrolyte. So, its enhancement is an indication that one of the complex species is adsorbed at the electrode snrface. 

Metal Halides. Reacts explosively or violently with the following calcium bromide iron(III) bromide or chloride iron(II) bromide or iodide cobalt(II) chloride silver fluoride all four mercury(II) halides copper(I) chloride, bromide or iodide copper(II) chloride and bromide ammonium tetrachlorocuprate zinc and cadmium chlorides, bromides, and iodides aluminum fluoride, chloride, and bromide thallium bromide tin(II) or (IV) chloride tin(IV) iodide arsenic trichloride and triiodide antimony and bismuth trichlorides, tribromides, and triiodides vanadium(V) chloride chromium(IV) chloride manganese(II) and iron(II) chlorides and nickel chloride, bromide, and iodide.17,22"25... 

Certain Lewis acids are known to induce an epoxide-aldehyde rearrangement <01TL8129>, and this chemistry has recently been combined in tandem with metal-mediated allylations. For example, epoxides react with tetraallyltin in the presence of bismuth(III) triflate to give homoallylic alcohols 116. The reaction involves an initial 1,2-shift to form an aldehyde 115, which is then attacked by the allyl tin species <03TL6501>. A similar but operationally more straightforward protocol is available by combining allyl bromide with indium metal, followed by the addition of epoxide <03TL2911>. 

Much remains to be done in the fleld of complexes of mixed ligands. All the ruthenium (III) 12) and rhodium (III) 126) chloro-aqua complexes have been separated by ion-exchange techniques, and the mixed complexes, OsClaBr6 a and IrClaBr6 a S by electrophoresis (7, 88). Labile mixed complexes such as bismuth (III) 78) and uranium (IV) 38) chloro-bromides have been studied by spectrophotometry, but the conclusions are obviously more difficult to obtain. 

Diorganoantimony and -bismuth(III) iodides have been prepared by the reaction of the corresponding chlorides or bromides with sodium or potassium iodide (equation 44) °. 

Acetylation, formylatlon, and benzoylation of a variety of primary and secondary alcohols with the respective acids (acetic acid or anhydride, ethyl formate, and benzoic anhydride) can be achieved under the catalysis of BiCls, Bi(OCOCF3)3, or Bi(OTf)3 (Scheme 14.97) [194—196]. The O-acylahon of phenols is also promoted by these Lewis acids. Among the bismuth(III) salts employed, Bi(OTf)3 is the most effechve in terms of reaction condihons and yields of the esters. The Bi(OTf)3-acid anhydride procedure is apphcable to the acylahon of sterically demanding or tertiary alcohols and phenols. Treatment of terhary or benzylic bromides with Bi(OCOR)3 (R=Me, Ph) affords the corresponding esters [197]. In the presence of a catalytic amount of 612(804)3, the esterificahon of cis-(-)-thujopsene with a series of C2-C8 acids proceeds in moderate yield [198]. 

Calcium(II), which shows no appreciable complexing, has a distribution coefficient of 147 in 0.5 M perchloric acid and 191 in 0.5 M hydrochloric acid. Strelow. Rethc-meyer, and Bothnia [10] also reported data for nitric and sulfuric acids that showed complexation in some cases. Mercury(II), bismuth(III), cadmium(II), zinc(II), and lead(II) form bromide complexes and are eluted in the order given in 0.1 to 0.6 M hydrobromic acid [11]. Most other metal cations remain on the column. Aluminu-m(III), molybdenum(VI), niobium(V), tin(IV), tantalum(V), uranium(VI), tung-sten(VI), and zirconium(IV) form anionic fluoride complexes and are quickly eluted from a hydrogen-form cation-exchange column with 0.1 to 0.2 M HF [12]. 

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