Bismuth trihalides

Bismuth salts, 4 25 Bismuth sesquisulfide, 4 24 Bismuth subcarbonate, 4 36 Bismuth subgallate, 4 36 Bismuth subhalides, 4 19 Bismuth subnitrate, 4 36 Bismuth subsalicylate, 4 1, 36 medical applications of, 22 11-12 Bismuth(III) sulfate, 4 25 Bismuth(III) sulfide, 4 24 Bismuth sulfides, 4 24-25 Bismuth thiolates, 4 25 Bismuth-tin alloy waterfowl shot, 4 15 Bismuth triacetate, 4 25 Bismuth tribromide, 4 21 physical properties of, 4 20t Bismuth trichloride, 4 19-20 physical properties of, 4 20t Bismuth trifluoride, 4 19 physical properties of, 4 20t Bismuth trihalides, 4 19 Bismuth triiodide, 4 21-22 physical properties of, 4 20t Bismuth trinitrate pentahydrate, 4 25 Bismuth trioxide, 4 23-24 physical properties of, 4 20t Bismuth triperchlorate pentahydrate, 4 25... 

Bismuth Halides. The bismuth trihalides are the best known. Bismuth does form a single pentahalide, BiF5, and subhalides that approximate the composition BiX, the best characterized of these being BiCl11(57. Vapors above solutions of a bismuth trihalide in molten bismuth contain the species BiX and/or (BiX)w, where X = Cl, Br, or I (9). At temperatures below 323°C, a black, diamagnetic, orthorhombic solid of the overall composition BiCl1 7 may be isolated from solutions of bismuth trichloride in molten bismuth (10). 

Direct halogenation of metallic bismuth yields bismuth pentafluoride in the case of fluorine, the corresponding bismuth trihalides for the other halogens. Reaction of bismuth trioxide with aqueous HF, HC1, or HBr yields the corresponding bismuth trihalide. Physical and thermochemical properties of the more important bismuth halides appear in Table 2. 

Triarylbismuthines have been synthesized by means of the Nesmeyanov reaction that employs an arenediazonium salt such as the tetrafluoroborate, a bismuth trihalide, and a reducing agent (51). The decomposition of iodonium salts in the presence of bismuth trichloride and metallic bismuth also leads to the formation of triarylbismuthines, Ar3Bi (52) ... 

The reaction of tris(trifluoromethyl)bismuthine with chlorine, bromine, or iodine, however, has been found to yield the corresponding bismuth trihalide and trifluoromethyl halide (61) ... 

Bismuth trihalides exhibit an increased tendency toward hydrolysis, usually forming bismuthyl compounds, also called bismuth oxyhalides,... 

Many trialkyl- and triaryl-bismuthines are known, although only a very small number have been used as ligands. References to specific BiR3 from earlier literature can be found in various reviews.9,10,12,15 The most widely used route is reaction of bismuth trihalide with the appropriate Grignard or organolithium reagent in diethyl ether or tetrahydrofuran. The air-stable... 

The preparation of 1 1 complexes of arsenic, antimony, and bismuth trihalides with dithio-oxamides has been reported.647 I.r. spectra of the arsenic compounds point strongly to the probability of dimeric, octahedral structures, but with the two heavier Group V elements square-pyramidal structures have been suggested. Crystalline adducts 2MBr3,3dioxan, where... 

Treatment of a bismuth trihalide with electron-rich arenes affords arene-BiX3 TT-complexes. When the reaction is carried out in the presence of AICI3, the corresponding cationic ir-complexes are formed [87AG(E)74]. The arenes employed so far are benzene, toluene, mesitylene, hexamethyl-benzene, perylene, pyrene, acenaphthene, phenanthrene, fluorene, and fluor-anthene-p-xylene (1/0.5). The isolated compounds are summarized in Table 2.29. 

Bismuth trihalides along with the analogous arsenic and antimony compound form complexes with metal carbonyls with bismuth, however, only neutral species such as Cl2BiFe(CO)2Cp and Bi[Co(CO)3PPh3l3 were isolated. 

Mansfeld and coworkers [127] described the synthesis and characterization of the one-to-one complexes of the bismuth trihalides BiXs (X= Cl, Br, I) with the chelating oxygen-coordinating-donor ligand (iso-PrO)2(0)PCH2P(0)(Oiso-Pr)2. The compounds were analyzed by single crystal XRD, IR, thermal analysis, NMR, ESI MS and conductivity measurements. The combination of these techniques gives a frill description of the structures in the solid state and in solution, and provides information about the use of phosphonic ester complexes as precursors for the formation of bismuth phosphonates. 

Triethylsilane can also facilitate the high yielding reductive formation of dialkyl ethers from carbonyls and silyl ethers. For example, the combination of 4-bromobenzaldehyde, trimethylsi-lyl protected benzyl alcohol, and EtsSiH in the presence of catalytic amounts of FeCls will result in the reduction and benzylation of the carbonyl group (eq 32). Similarly, Cu(OTf)2 has been shown to aid EtsSiH in the reductive etherification of variety of carbonyl compounds with w-octyl trimethylsilyl ether to give the alkyl ethers in moderate to good yields. Likewise, TMSOTf catalyzes the conversion of tetrahydrop)ranyl ethers to benzyl ethers with Ets SiH and benzaldehyde, and diphenylmethyl ethers with EtsSiH and diphenylmethyl formate. Symmetrical and unsymmetrical ethers are afforded in good yield from carbonyl compounds with silyl ethers (or alcohols) and EtsSiH catalyzed by bismuth trihalide salts. An intramolecular version of this procedure has been nicely applied to the construction of cA-2,6-di- and trisubstituted tetrahydropyrans. ... 

The heavier phosphorus trihaUdes (PX3, X = Cl, Br, I) are prepared by direct halogenation. The trifluoride, on the other hand, is best synthesized by treating the trichloride with an ionic fluoride such as CaF2 or ZnF2- The arsenic, antimony, and bismuth trifluorides are prepared by adding hydrogen fluoride to the oxides. (If fluorine gas is used, the pentafluorides result.) The other trihalides of arsenic and antimony can be produced by direct halogenation of either the elements or the trioxides, while the bismuth trihalides are best produced by the action of aqueous hydrohalic acids on 61203. 

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