Fluorosulfates synthesis

Chlorine trifluoromethanesulfonate, which is much less stable than the corresponding fluorosulfate was synthesized by the reaction of triflic acid with ClF [35]. In the synthesis of bromine trifluoromethansulfonate, the reaction of C10S02CF3 with Br2 was used [36]. 

The first publication on addition of BrOS02F to several fluoroolefins, which appeared in 1966 [103], was followed by a communication on the reaction of chlorine and bromine fluorosulfate with HFP [97]. This initiated the appearance of a number of papers on the use of halogen fluorosulfates in fluoroorganic synthesis. Most of these publications came from Professor Fokin s group in the former Soviet Union. 

Fokin AV, Studnev Yu N (1984) Some Aspects of the Use of Peroxydisulfuryl Difluoride and Halogen Fluorosulfates in Organic Synthesis. In ibid p 47... 

Compounds which are vanishingly weakly basic in H20, such as nitro-anilines, nitro-aromatic or halo-nitro-aromatic compounds are protonated to a greater or less extent in superacids, allowing them to be used as indicators in Hammett Acidity Function measurements. Cl- which has essentially zero base strength in H20 is protonated by the superacids to HC1, which being monomolecular is expelled as a gas from the highly associated solvents. This provides a commonly-used important route to synthesis of anhydrous fluorides, fluorosulfates and triflates. 

In an extensive and critical review of the synthesis and properties of transition metal fluorosulfates and triflates, Aubke, Cader and Mistry [25] state that the only known molecular structure amongst the fluorosulfates is the dimeric Au(S03F)3, the rest being associated solids. 

Synthesis of inorganic triflates has been restricted almost entirely to metathetical or solvolysis reactions [25] and only a very small number of ionic inorganic species has been generated in CF3S03H [24], Many more binary fluorosulfates and several... 

Chlorine fluorosulfate is a pale yellow liquid that solidifies at —84.3° and boils at 43.4°. The IR spectrum of the gas has bands at 1481 (vs), 1248 (vs), 855 (vs), 831 (ms, sh), 703 (ms), 572 (ms), and 529 (m) cm (stainless steel cell with AgQ windows). Chlorine fluorosulfate is the only known practical intermediate for the synthesis of chlorine perchlorate, ClOClOj, and it is easily photolyzed in Pyrex at room temperature to provide FOjSOOSO F in high yield." Chlorine fluorosulfate reacts violently with water. 

Synthesis of Fluorosulfates. The chemical behavior of F2S2O6 is determined by two features of its reactivity (a) the ability to generate the radical species OS02F in the reversible... 

Recently, the concept of inductive effect have been applied to replace (P04) for (804) in polyanionic cathode materials [35, 36, 93-119]. Table 8.3 summarizes the structural properties of some fluorosulfate compoxmds. The fluorosulfates LLMSO4F constitute a wide family showing a good mix of properties, especially, both electrochemical and safety issues. However, we notice that the electroactive compounds appeared only in 2010 after the synthesis of newest member of the tavorite family LiFe (S04)F [36]. For instance, a simple substitution in Nasicon Li cM3(X04)3 networks increases the redox potential by 800 mV independently of the 2>d transition-metal ion [2]. Recent review by Rousse and Tarascon [119] deals with the crystal chemistry and structural-electrochemical relationship of new fluorosulfate polyanionic LiMS04p electrode materials. The lithiated fluorosulfates present an interesting family from the view point of crystal chemistry with the three main types of structure that depend on the nature of the transition-metal ion ... 

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