Lewis antimony pentafluoride

My work on long-lived (persistent) carbocations dates back to the late 1950s at Dow and resulted in the first direct observation of alkyl cations. Subsequently, a wide spectrum of carbocations as long-lived species was studied using antimony pentafluoride as an extremely strong Lewis acid and later using other highly acidic (superacidic) systems. 

Lewis Acid Complexes. Sulfolane complexes with Lewis acids, such as boron trifluoride or phosphoms pentafluoride (17). For example, at room temperature, sulfolane and boron trifluoride combine in a 1 1 mole ratio with the evolution of heat to give a white, hygroscopic soHd which melts at 37°C. The reaction of sulfolane with methyl fluoride and antimony pentafluoride inhquid sulfur dioxide gives crystalline tetrahydro-l-methoxythiophenium-l-oxidehexafluoroantimonate, the first example of an alkoxysulfoxonium salt (18). 

Antimony pentafluoride is a strong Lewis acid and a good oxidizing and fluorinating agent. Its behavior as a Lewis acid leads to the formation of numerous simple and complex adducts. It reacts vigorously with water to form a clear solution from which antimony pentafluoride dihydrate [65277-49-8], SbF 2H2O, may be isolated. This is probably not a tme hydrate, but may well be better formulated as [H O] [SbF OH]. 

Grown Ethers. Ethylene oxide forms cycHc oligomers (crown ethers) in the presence of fluorinated Lewis acids such as boron tritiuoride, phosphoms pentafluoride, or antimony pentafluoride. Hydrogen fluoride is the preferred catalyst (47). The presence of BF , PF , or SbF salts of alkah, alkaline earth, or transition metals directs the oligomerization to the cycHc tetramer, 1,4,7,10-tetraoxacyclododecane [294-93-9] (12-crown-4), pentamer, 1,4,7,10,13-pentaoxacyclopentadecane [33100-27-6] (15-crown-6), andhexamer, 1,4,7,10,13,16-hexaoxacyclooctadecane [17455-13-9]... 

Reactions of organoxenonium salts [RXe][EFn+)] with Lewis acids do not result in transformation of the organo group of the cation [RXe]+ (6), but rather give rise to fluoride abstraction from the counteranion [EFn+i]. For example, organoxenonium fluoroborates were converted into [EF6]" salts by using arsenic or antimony pentafluoride or their adducts, EFj L (eqs 9, 10) (22, 30). 

In earlier days it was fairly common to suggest that sulfenium ions, RS+, were involved as intermediates in a number of these substitutions, particularly those in which sulfenyl halides RSX reacted with very weak nucleophiles, or those where electrophilic catalysis of the substitution was observed (Parker and Kharasch, 1959). However, it has since become evident (Owsley and Helmkamp, 1967 Helmkamp et al., 1968 Capozzi et al., 1975) that sulfenium ions are almost impossible to generate as intermediates. For example, Capozzi et al., (1975) showed that although treatment of a sulfenyl chloride RSC1 with the powerful Lewis acid antimony pentafluoride led to the complete conversion of the sulfenyl chloride to a cation, what was formed was, not the sulfenium ion RS+, but rather the cation [59] in reaction (172). These results, and others... 

Olah and co-workers in 1963 flrst observed the formation of stable alkylcarbonium ion complexes when t-butyl fluoride was dissolved in excess antimony pentafluoride (serving as both the Lewis acid and the solvent). 

It was indeed found necessary to have excess antimony pentafluoride present in order to obtain stable alkylcarbonium hexafluoroantimonate complexes. Antimony pentafluoride is a liquid Lewis acid fluoride (b.p. 148-150°) of low dielectric constant (e 3), which has been shown by fluorine N.M.R. studies in the pure liquid state and in solution to exist in both cyclic and acyclic polymeric forms involving fluorine bridges. The antimony is in approximately octahedral co-ordination with predominant bridging by coordinating fluorines (Gillespie and Rothenbury, 1963). As fluorine generally does not show bridging properties, the structure of antimony pentafluoride itself indicates the very... 

If, however, the reaction is run in the presence of a Lewis acid, particularly antimony pentafluoride, the reaction takes a different course, giving a diacyl cyclopropane. 

The order of decreasing Lewis basicity toward trimethylaluminum is thiane, thiolane, diethyl (or dimethyl) sulfide, thietane and 2-methylthiirane (67IC1461). Thietane can be protonated at -60 °C with fluorosulfonic acid in antimony pentafluoride-liquid sulfur dioxide the NMR spectrum shows bands at 8 7.40 (S—H) and 3.20-4.40 p.p.m. (C—H) (71JOC1121). 

Antimony pentafluoride (SbF5) is a strong Lewis acid, so the equilibrium... 

More recently, development of the superacid solvent systems has permitted the preparation at low temperature of stable solutions of carbocations of many structural types. The solvents ordinarily used consist of the strong Lewis acid antimony pentafluoride with or without an added protonic acid, usually hydro-... 

Internal polyfluoroalkenes are less reactive toward S03. Indeed, fluorosulfate was obtained in low yield in reaction of F-2-butene and S03 and BF3 at 150°C [175]. However, much better results were achieved when a stronger Lewis acid was employed. Interaction of internal F-olefins with S03 stabilized by antimony pentafluoride proceeds at 75-80°C resulting in the corresponding fluorosulfates 89a-e [178,179] ... 

SbCla is a relatively weak Lewis acid, since in the presence of a mixture of mesity-lene and benzoyl chloride it gives a complex with mesitylene Antimony penta-chloride is stronger and gives a 1 1 complex with perylene whose electronic spectrum is similar to that of the perylene cation Complexation has been claimed between antimony pentafluoride and aromatic olefins such as 1,1-diphenylethylene and stilbene ... 

Lewis acid-promoted cyclopropanation of a,) -unsaturated carbonyl compounds by a-diazoketones has been reported to yield 1,2-diacylcyclopropanes of high isomeric purity. Isomerization of these derivatives by antimony pentafluoride produced the more stable geometrical isomer 141 (equation 35). ... 

Solid superacids may be made by treating ordinary solid acid catalysts with strong Br0nsted or Lewis acids. For example, if freshly precipitated titanium hydroxide or zirconium hydroxide is treated with sulfuric acid and calcined in air at 500 °C. a very active solid acid catalyst results. The solids consist mainly of the metal dioxides with sulfate ions coordinated to the metal ions on the surface. Likewise, a superacid solid catalyst can be made by treating these metal oxides with antimony pentafluoride. Both catalysts contain both Brpnsted and Lewis acid sites, and they are sufficiently active to catalyze the isomerization of n-butane at room temperature.- ... 

A purely chemical synthesis of elemental fluorine was achieved by K. O. Christe in 1986 [10] (Scheme 1.1), just in time for the 100 year anniversary of Moissan s first electrochemical fluorine synthesis. Nevertheless, in his paper Christe remarks that all the basic know-how required for this work had already been available 50 years earlier. The key to his simple method is a displacement reaction between potassium hexafluoropermanganate [11] with the strongly fluorophilic Lewis acid antimony pentafluoride at 150 °C. 

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