Fluorination halogen fluorides

The reactivity of fluorine compounds varies from extremely stable, eg, compounds such as sulfur hexafluoride [2551-62 ] nitrogen trifluoride [7783-54-2] and the perfluorocarbons (see Fluorine compounds, organic) to extremely reactive, eg, the halogen fluorides. Another unique property of nonionic metal fluorides is great volatiUty. Volatile compounds such as tungsten hexafluoride [7783-82-6] molybdenum hexafluoride [7783-77-9] ... 

Fluorine forms very reactive halogen fluorides. Reaction of CI2 and F2 at elevated temperatures can produce GIF, CIF, or CIF 3 be obtained from the reaction of Br2 and F2. These halogen fluorides react with all nonmetals, except for the noble gases, N2, and O2 (5). Fluorine also forms a class of compounds known as hypofluorites, eg, CF OF (6). Fluorine peroxide [7783-44-0], O2F2, has also been reported (6). 

The halogen fluorides are binary compounds of bromine, chlorine, and iodine with fluorine. Of the eight known compounds, only bromine trifluoride, chlorine trifluoride, and iodine pentafluoride have been of commercial importance. Properties and appHcations have been reviewed (1 7) as have the reactions with organic compounds (8). Reviews covering the methods of preparation, properties, and analytical chemistry of the halogen fluorides are also available (9). 

The halogen fluorides are best prepared by the reaction of fluorine with the corresponding halogen. These compounds are powerful oxidising agents chlorine trifluoride approaches the reactivity of fluorine. In descending order of reactivity the halogen fluorides are chlorine pentafluoride [13637-63-3] 1 5 chlorine trifluoride [7790-91-2] 3 bromine pentafluoride [7789-30-2], BrF iodine heptafluoride [16921 -96-3], chlorine... 

Water reacts violently with aH halogen fluorides. The hydrolysis process can be moderate by cooling or dilution. In addition to HF, the products may include oxygen, free halogens (except for fluorine), and oxyhalogen acids. 

Equipment should be carefiiUy and completely degreased and passivated with low concentrations of fluorine or the gaseous halogen fluoride before use. Special care should be taken that valves are completely disassembled and each part carefiiUy cleaned. 

Carbon-nitrogen multiple bonds in fluorinated imines and nitriles react with halogen fluoride reagents Imines provide 7V-chloroamine.s on reaction with chlo rme fluoride [62, 121, 122, 123] (equations 23 and 24) or with cesium fluoride and chlorine [124] and A -bromoammes on reaction with cesium fluoride and bromine (equation 24)... 

Because of the size of the iodine atom and the fact that it is easier to oxidize to the +7 state, IF7 is the only XX 7 interhalogen. It is prepared by the reaction of IF5 and F2 at elevated temperatures, and like other halogen fluorides it is a strong fluorinating agent. When it reacts with water, HF and HI04 are produced. 

Fluorofullerenes have been prepared by reaction with halogen fluorides, by direct fluorination with F2 or by fluorination with noble gas fluorides [7,8,14], The reaction with high valence metal fluorides is the most versatile route for the synthesis of CsoFnH. 

Fluorination with Noble Cas Fluorides and Halogen Fluorides... 

In the same way a number of other substances dissolved and, on evaporation of excess solvent, gave residues which could likewise be formulated Jis acids (Table 1). It will be noted that the halogen fluoride has a dual role, and first functions as a fluorinating agent before reacting with the fluorinated product to form the acid. 

Fluorine also reacts with other halogens, forming interhalogen compounds. While with bromine and iodine it reacts vigorously at ordinary temperatures, with chlorine the reaction occurs at 200°C. Such interhalogen products with these halogens include iodine heptafluoride, bromine trifluoride, bromine pentafluoride, and chlorine trifluoride. Metalloid elements, such as arsenic, silicon, selenium, and boron also inflame in a stream of fluorine, forming fluorides. 

Fluorine is the most energetic oxidizing element and as such is of prime importance in advanced oxidizers. The fluorine-based oxidizers discussed here include elemental fluorine, compounds containing oxygen and fluorine, nitrogen-fluorine compounds, halogen fluorides, and noble gas fluorides. 

For a review of mixed halogenations where one side is fluorine, see Sharts Sheppard Org. React. 1974, 21, 125-406. pp. 137-157. See also German Zemskov, Ref. 612. For a review of halogen fluorides in organic synthesis, sec Boguslavskaya 7 uss. Chem. Rev. 1984, 53, 1178-1194. 

A very diversified art has been developed utilizing certain metal fluorides, inorganic fluorides, halogen fluoride, or electrochemical cells as media for fluorination. The more important approaches which have been developed to produce fluorocarbons and yet avoid the great reactivity of elemental fluorine are ... 

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