SbCls

Antimony peniachloride, SbCls. M.p. TC, b.p. 79 C (Sb or SbCIa plus CI2). Readily hydrolysed by water, forms complexes, e.g. [SbClft]". Mixed antimony(III)/(V) complexes occur as salts M2SbCl6. SbCls is used extensively as a chlorinating agent. 

Donor strengths, taken from ref. 207b, based upon the solvent effect on the symmetric stretching frequency of the soft Lewis acid HgBr2. Gutmann s donor number taken from ref 207b, based upon AHr for the process of coordination of an isolated solvent molecule to the moderately hard SbCL molecule in dichioroethane. ° Bulk donor number calculated as described in ref 209 from the solvent effect on the adsorption spectrum of VO(acac)2. Taken from ref 58, based on the NMR chemical shift of triethylphosphine oxide in the respective pure solvent. Taken from ref 61, based on the solvatochromic shift of a pyridinium-A-phenoxide betaine dye. 

Antimony tnfluoride is a mild fluorinating reagent. However, it is much mote effective ia the Swarts reactions where its effectiveness as a fluorinating reagent is dramatically iacteased by addition of CI2, Bt2, or SbCl to the reaction mixture (2). Antimony tnfluotide can be used for the replacement of chlorine or bromine ia halocatbons, hydtohalocatbons, and nonmetal and metal haUdes. Typical reactions can be summarized as follows ... 

The effectiveness of antimony fluoride is increased if it is used in conjunction with chlorine or with antimony pentachloride. The formation of either SbCl2F2 or a complex of SbF and SbCl probably accounts for the increased activity (4). 

Atertiary amines, AsCl, FeCl, BF, TiCl, TiF, BiCl, SbCl, and SbCl. The most widely used protic acid catalysts are HCl, H2SO4, H PO, ... 

BeCl2, CdCl, ZnCl2, BF, BCl, BBr, GaCl, GaBr, TiCl, ZrCl, SnCl, SnBr, SbCl, SbCl, BiCl, FeCl, and UCl. ... 

Particular drawbacks of using alkylsiHcon and alkyltin haHdes with AlCl for the cationic polymerization of terpenes are low yields and the fact that they require rigorously dried feeds (<50 ppm H2O) to be effective. Increased water content results in lower yields and lower softening points (85). Catalyst systems comprised of AlCl with antimony haHdes in the presence or absence of a lower alkyl, alkenyl, or aralkyl haHde are particularly effective in systems containing up to 300 ppm H2O (89,90). Use of 2—12 wt % of a system composed of 2—3 parts AlCl, 0.7—0.9 parts SbCl, and 0—0.2 parts of an organic... 

PoIysuIfonyIa.tlon, The polysulfonylation route to aromatic sulfone polymers was developed independendy by Minnesota Mining and Manufacturing (3M) and by Imperial Chemical Industries (ICI) at about the same time (81). In the polymerisation step, sulfone links are formed by reaction of an aromatic sulfonyl chloride with a second aromatic ring. The reaction is similar to the Friedel-Crafts acylation reaction. The key to development of sulfonylation as a polymerisation process was the discovery that, unlike the acylation reaction which requires equimolar amounts of aluminum chloride or other strong Lewis acids, sulfonylation can be accompHshed with only catalytic amounts of certain haUdes, eg, FeCl, SbCl, and InCl. The reaction is a typical electrophilic substitution by an arylsulfonium cation (eq. 13). 

The hexachloride, uranium hexachloride [13763-23-0], UCl, is best prepared by chlorination of UCl [10026-10-5] with SbCl. An alternative preparative approach is the disproportionation UCl [13470-21 -8] to UCl and UCl under reduced pressure. The obvious disadvantage of the second method is contamination by UCl, however, sublimation is a possible purification technique. Isostmctural with the hexafluoride, the hexachloride is monomeric with an octahedral arrangement of the chlorine atoms around the uranium center. 

The classical synthesis iavolves the dissolution of a 33% Sb—67% Zn alloy by hydrochloric acid the evolved gases contain up to 14% stibiae. A detailed procedure usiag a Sb—Mg alloy has also beea described (16). Aluminum hydride or alkaU metal borohydrides have been used to reduce antimony(III) ia acidic aqueous solutioa to produce stibiae. A 23.6% yield of stibiae, based oa the borohydride used, has beea reported (17). A 78% yield based oa Sb has beea obtaiaed by gradually adding a solutioa that is 0.4 Min SbCl and saturated ia NaQ, to aqueous NaBH at mol ratios of NaBH iSbQ. >10 (18). 

Antimony trichloride is used as a catalyst or as a component of catalysts to effect polymerisation of hydrocarbons and to chlorinate olefins. It is also used in hydrocracking of coal (qv) and heavy hydrocarbons (qv), as an analytic reagent for chloral, aromatic hydrocarbons, and vitamin A, and in the microscopic identification of dmgs. Liquid SbCl is used as a nonaqueous solvent. 

Both antimony tribromide and antimony ttiiodide are prepared by reaction of the elements. Their chemistry is similar to that of SbCl in that they readily hydroly2e, form complex haUde ions, and form a wide variety of adducts with ethers, aldehydes, mercaptans, etc. They are soluble in carbon disulfide, acetone, and chloroform. There has been considerable interest in the compounds antimony bromide sulfide [14794-85-5] antimony iodide sulfide [13868-38-1] ISSb, and antimony iodide selenide [15513-79-8] with respect to their soHd-state properties, ferroelectricity, pyroelectricity, photoconduction, and dielectric polarization. 

Antimony pentafluoride may be prepared by fluorination of SbF or by treatment of SbCl with HF. In the latter method the fifth chlorine is removed with difficulty failure to remove the chlorine completely results in contamination of the distilled SbF with Sb(III) (27). 

When a diazonium salt is allowed to react with antimony pentachloride or an aryltetrachloroantimony compound, the onium salts [ArN2] [SbClg] or [ArN2] [Ar SbCl ], respectively, are formed. These can be decomposed ia an organic solvent by the addition of a powdered metal such as iron or ziac, with the formation of a diaryltrichloroantimony compound ... 

Hydrochloric acid digestion takes place at elevated temperatures and produces a solution of the mixed chlorides of cesium, aluminum, and other alkah metals separated from the sUiceous residue by filtration. The impure cesium chloride can be purified as cesium chloride double salts such as cesium antimony chloride [14590-08-0] 4CsCl SbCl, cesium iodine chloride [15605 2-2], CS2CI2I, or cesium hexachlorocerate [19153 4-7] Cs2[CeClg] (26). Such salts are recrystaUized and the purified double salts decomposed to cesium chloride by hydrolysis, or precipitated with hydrogen sulfide. Alternatively, solvent extraction of cesium chloride direct from the hydrochloric acid leach Hquor can be used. 

FeCl, AlCl, or SbCl and organic sulfur compounds 2.2-3.3 17... 

Typical Lewis acids like BF3 and SbCls coordinate with oxirane oxygen to give (presumably) a cyclic oxonium ion (41) which reacts further (Scheme 28) (64HC 19-1)446, B-67MI50505). 

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