Antimony fluoride halides

CsCl HgCl2=3 1, 2 1, 1 1, 2 3, 1 2, and 1 5 and five caesium antimonious fluorides where CsF SbF3=l 1, 3 4, 4 7, 1 2, and 1 3. According to I. Remsen s rale (1889) When a halide of any element combines with a halide of an alkali metal to form a double salt, the number of molecules of the alkali salt which are added to one molecule of the other halide is never greater, and is generally less than the number of halogen atoms contained in the latter—for instance, in the double fluoride of sodium and aluminium, where the negative halide has three fluorine atoms, no more than three molecules of sodium fluoride will be found united with one of aluminium fluoride. 

Antimony(III) halides are chemically reactive, but less so than their phosphorus or arsenic analogues. Antimony(III) chloride forms a clear solution with water, and there is no evidence for Sb3+ ions dilution results in precipitation of insoluble oxychlorides of various compositions, e.g. SbOCl, Sb405a2, SbsOuCl2. Some reactions of SbCl3 are shown in Scheme 3. Antimony(III) fluoride is an important fluorinating agent. 

A very reactive halogen atom, such as that of mi acyl or sulfonyl halide, is replaced by fluorine by the action of almost any inorganic fluoride. The most convenient method consists in heating gently a mixture of an acyl or sulfonyl chloride with zinc or antimony fluoride in an apparatus which permits the acyl fluoride to distil as it is formed. The acyl fluoride usually boils about 40° lower than the chloride, and its removal from the reaction mixture results in quantitative yields. Com- plete interchange also can be effected with hydrogen fluoride, but more elaborate equipment is required. Good results have been reported for the synthesis of formyl and acetyl fluorides from mixtures of fonnic or... 

Hydrogen fluoride alone undergoes exchange reactions only with very reactive organic halides. However,. because it reacts with antimony chloride to form antimony fluoride and hydrogen chloride,34 it can be used to transform a large amount of organic halide to the fluoride with the aid of only small.amounts of antimony salts. This is the method used in industry for the preparation of dichlorodifluoromethane.34-36... 

This area has not been reviewed extensively before although Davidovich and Buslaev (2) have considered the coordination chemistry of bismuth in a general way, in which the structures of halides and halogenoanions are featured. Sawyer and Gillespie (3) have commented previously upon the stereochemistry of antimony(III) halides (mostly fluorides). 

This point is illustrated by the silyl halides, whose properties are greatly affected by the presence of a silicon-silicon bond. The preparation of the chloride, bromide and iodide of monosilane is described above the fluoride is made by the action of the chloride on antimony fluoride ... 

Other catalysts which may be used in the Friedel - Crafts alkylation reaction include ferric chloride, antimony pentachloride, zirconium tetrachloride, boron trifluoride, zinc chloride and hydrogen fluoride but these are generally not so effective in academic laboratories. The alkylating agents include alkyl halides, alcohols and olefines. 

In a generalized sense, acids are electron pair acceptors. They include both protic (Bronsted) acids and Lewis acids such as AlCb and BF3 that have an electron-deficient central metal atom. Consequently, there is a priori no difference between Bronsted (protic) and Lewis acids. In extending the concept of superacidity to Lewis acid halides, those stronger than anhydrous aluminum chloride (the most commonly used Friedel-Crafts acid) are considered super Lewis acids. These superacidic Lewis acids include such higher-valence fluorides as antimony, arsenic, tantalum, niobium, and bismuth pentafluorides. Superacidity encompasses both very strong Bronsted and Lewis acids and their conjugate acid systems. 

Isomerization of fluoroolefins by a shift of a double bond is catalyzed by halide 10ns [7] The presence of crown ether makes this reaction more efficient [74] Prolonged reaction time favors the rearranged product with an internal double bond (equations 3-5) Isomerization of perfluoro-l-pentene with cesium fluoride yields perfluoro-2-pentenes in a Z ratio of 1 6 [75] Antimony pentafluoride also causes isomenzation of olefins leading to more substituted products [76]... 

Antimony dichloride trifluoride, 3 62t Antimony dioxide, 3 59 Antimony graphite fluoride, 3 63-64 Antimony halides, physical properties of, 3 61t... 

Rubidium metal alloys with the other alkali metals, the alkaline-earth metals, antimony, bismuth, gold, and mercury. Rubidium forms double halide salts with antimony, bismuth, cadmium, cobalt, copper, iron, lead, manganese, mercury, nickel, thorium, and zinc. These complexes are generally water insoluble and not hygroscopic. The soluble rubidium compounds are acetate, bromide, carbonate, chloride, chromate, fluoride, formate, hydroxide, iodide,... 

The first long-lived fluorine-containing carbocation was discovered by Olah and coworkers.32 Thus, the fluorodimethylcarbcnium ion [Me2CF+] was obtained by protonation of 2-fluoropropene and also from 2,2-difluoropropane by reaction with antimony(V) fluoride. In the course of these investigations it was found that a-F stabilizes a cationic state, whereas fi-F is destabilizing. Attempts to prepare the simplest member of this class, the trifluoromethyl carbocation CF3+ failed. The ionization of trifluoromethyl halides with antimony(V) fluoride at — 80 C yielded only carbon tetrafluoride. 

Aluminum trichloride and boron trifluoride as additives have a similar effect on the fluorination of (trichloromethyl)benzene by antimony(III) fluoride. With the additives, the reaction starts even at O C but no exchange is observed in the absence of the catalysts.12 The relative exchange reactivity order of the antimony halides is as follows antimony(III) fluoride < anti-mony(III) fluoride + antimony/V) chloride < antimony(V) dichlorotrifluoride, antimony/V) di-bromotrifluoride < antimony/V) fluoride.3... 

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