Silver fluorine

Chromic acid, nitric acid, hydroxyl-containing compounds, ethylene glycol, perchloric acid, peroxides, or permanganates Concentrated nitric and sulphuric acid mixtures Chlorine, bromine, copper, silver, fluorine or mercury Carbon dioxide, carbon tetrachloride, or other chlorinated... 

The heterobimetallic compounds 79-83 comprise Ag(I)-Sn(II) covalent bonds, with similar Ag—Sn bonding distances (Table 2.11.3). In particular, compounds 79 and 80 give dimeric arrangements, while in for 81-83, the use of silver fluorinated tris(pyrazolyl)borates and tin(II) N-alkyl-2-(alkylamino)troponiminates allow the isolation of monomeric compounds. 

Disilver fluoride is a bronze-colored compound with a greenish cast when observed in bulk. It is an excellent electrical conductor. Crystal-structure determination3 shows the complete absence of elemental silver and silver(I) fluoride in the pure material and reveals the presence of successive layers of silver, silver, and fluorine in the lattice. The silver-silver distance is 2.86 A. (nearly twice the metallic radius of 1.53 A.), and the silver-fluorine distance is 2.46 A. [as in ionic silver(I) fluoride]. The compound is regarded as being intermediate in structure between a metal and a salt.4... 

Katsikogianni M, et al. Adhesion of slime producing Staphylococcus epidermidis strains to PVC and diamond-like carbon/silver/fluorinated coatings. J Mater Sci Mater Med 2006 17(8) 679-89. 

The materials examined were high and low density polyethylene, silvered fluorinated ethylene propylene teflon blanket material, polysulphone matrix resin/graphite fibre reinforced composites, poly(methyl methacrylate) and silicones [326, 450,1326, 2314]. Long term exposed polymeric samples show loss of surface integrity and surface erosion. The radiation combines with atomic oxygen to initiate chain scission and crosslinking, both of which greatly affect the polymers structural properties. 

Black silver(II) fluoride, AgF2 (Ag 4- F2), is a strong fluorinating agent. 

Bromine has a lower electron affinity and electrode potential than chlorine but is still a very reactive element. It combines violently with alkali metals and reacts spontaneously with phosphorus, arsenic and antimony. When heated it reacts with many other elements, including gold, but it does not attack platinum, and silver forms a protective film of silver bromide. Because of the strong oxidising properties, bromine, like fluorine and chlorine, tends to form compounds with the electropositive element in a high oxidation state. 

Also, in anhydrous conditions, silver reacts with fluorine and forms silver difluoride AgFj and cobalt gives cobalt(III) fluoride, C0F3, these metals showing higher oxidation states than is usual in their simple salts. 

Halogens can act as ligands and are commonly found in complex ions the ability of fluorine to form stable complex ions with elements in high oxidation states has already been discussed (p. 316). However, the chlorides of silver, lead(Il) and mercury(l) are worthy of note. These chlorides are insoluble in water and used as a test for the metal, but all dissolve in concentrated hydrochloric acid when the complex chlorides are produced, i.e. [AgCl2] , [PbC ] and [Hg Clj]", in the latter case the mercury(I) chloride having also disproportionated. 

The only important compound is the paramagnetic silver(II) fluoride, AgFj, prepared by fluorination of the metal it is used as a convenient fluorinating agent. 

Acetylene Bromine, chlorine, brass, copper and copper salts, fluorine, mercury and mercury salts, nitric acid, silver and silver salts, alkali hydrides, potassium metal... 

Bromine Ammonia, carbides, dimethylformamide, fluorine, ozone, oleflns, reducing materials including many metals, phosphine, silver azide... 

Iodine Acetaldehyde, acetylene, aluminum, ammonia (aqueous or anhydrous), antimony, bromine pentafluoride, carbides, cesium oxide, chlorine, ethanol, fluorine, formamide, lithium, magnesium, phosphorus, pyridine, silver azide, sulfur trioxide... 

Fluorspar occurs in two distinct types of formation in the fluorspar district of southern Illinois and Kentucky in vertical fissure veins and in horizontal bedded replacement deposits. A 61-m bed of sandstone and shale serves as a cap rock for ascending fluorine-containing solutions and gases. Mineralizing solutions come up the faults and form vein ore bodies where the larger faults are plugged by shale. Bedded deposits occur under the thick sandstone and shale roofs. Other elements of value associated with fluorspar ore bodies are zinc, lead, cadmium, silver, germanium, iron, and thorium. Ore has been mined as deep as 300 m in this district. 

Uses. Silver fluoride has found many laboratory and special industrial appHcations. It is used as a soft (nHld) fluorinating agent for selective fluorination (7—17), as a cathode material in batteries (qv) (18), and as an antimicrobial agent (19). Silver fluoride is commercially available from Advance Research Chemicals, Inc., Aldrich Chemicals, Cerac Corp., Johnson/Matthey, PCR, Atochem, and other sources in the United States. The U.S. price of silver fluoride in 1993 was 1000— 1400/kg and the total U.S. consumption was less than 200 kg/yr. 

Silver difluoride [7783-95-1], AgF2, is a black crystalline powder. It has been classified as a hard fluorinating agent (3) which Hberates iodine from KI solutions and o2one from dilute aqueous acid solutions on heating. It spontaneously oxidizes xenon gas to Xe(II) in anhydrous hydrogen fluoride solutions (20). 

AgF2 is prepared by the action of elemental fluorine on AgF or AgCl at 200°C. Both processes result in quantitative yields. Silver difluoride should be stored in Teflon, passivated metal containers, or in sealed quartz tubes. 

However, the peroxomonophosphate ion decomposes relatively rapidly ia aqueous solution. A mixture of peroxodiphosphoric and peroxomonophoshoric acids can be produced by treatiag a cold phosphoric acid solution with elemental fluorine (qv) (49). Peroxodiphosphoric acid is not produced commercially. Ammonium, lithium, sodium, potassium, mbidium, cesium, barium, 2iac, lead, and silver salts have all been reported. The crystal stmctures of the ammonium, lithium, sodium, and potassium compounds, which crysta11i2e with varyiag numbers of water molecules, have been determined (50). 

Silver Fluoride. Silver fluoride, AgF, is prepared by treating a basic silver salt such as silver oxide or silver carbonate, with hydrogen fluoride. Silver fluoride can exist as the anhydrous salt, a dihydrate [72214-21-2] (<42° C), and a tetrahydrate [22424-42-6] (<18° C). The anhydrous salt is colorless, but the dihydrate and tetrahydrate are yellow. Ultraviolet light or electrolysis decomposes silver fluoride to silver subfluoride [1302-01 -8] Ag2p, and fluorine. 

Silver(III) Compounds. No simple silver(Ill) compounds exist. When mixtures of potassium or cesium haUdes are heated with silver hahdes ia a stream of fluorine gas, yellow KAgF [23739-18-6] or CsAgF [53585-89-0] respectively, are obtained. These compounds are diamagnetic and extremely sensitive to moisture (21). When Ag2S04 is treated with aqueous potassium persulfate ia the presence of ethylenedibiguanidinium sulfate, the relatively stable Ag(Ill)-ethylenebiguanide complex is formed. 

Alkyl fluorides have been prepared by reaction between elementary fluorine and the paraffins, by the addition of hydrogen fluoride to olefins, by the reaction of alkyl halides with mercurous fluoride, with mercuric fluoride, with silver fluoride, or with potassium fluoride under pressure. The procedure used is based on that of Hoffmann involving interaction at atmospheric pressure of anhydrous potassium fluoride with an alkyl halide in the presence of ethylene glycol as a solvent for the inorganic fluoride a small amount of olefin accompanies the alkyl fluoride produced and is readily removed by treatment with bromine-potassium bromide solution. Methods for the preparation of alkyl monofluorides have been reviewed. ... 

Up to 20 products with different numbers of fluorine atoms and double bonds have been isolated from the fluonnation of benzene with silver difluoride [d], manganese trifluoride [7], potassium tetrafluoroargentate [d], and potassium hexafluoronickelate [24] The composition of the products depends on the fluorinating agents and on the temperature (Table 1)... 

Table 1. Comparison of Fluorination of Benzene with Manganese Trifluoride [7], Potassium Hexafluoronickelate [24], Silver Difluoride [6], and Potassium Tetrafluorocobaltate [6]...

This topic has been reviewed [2, pp 94, 100-111, 130-134] All of the standard approaches to the synthesis of a compound like methyl 2-fluorostearate from methyl 2-bromostearate result mall yield of the 2-fluoro ester and the unsaturated esters. Although silver fluoride is not a new reagent, its use moist in wet acetonitrile to convert methyl 2-bromostearate to its fluoro ester is a departure from the traditional set of anhydrous conditions (Procedure 6, p 194) [71] In contrast, silver tetrafluoroborate converts a-chloroketones to their respective fluoroketones under anhydrous conditions. The displacement of less activated halogen groups by silver tetrafluoroborate to form their respective fluorides is novel Although silver tetrafluoroborate could not be used to convert an aliphatic terminal dichloromethyl or trichloromethyl group to its corresponding fluoro derivative, it is an effective fluorine source in other situations [72] (Table 8)... 

A recently discovered variant of the Wallach technique is the silver ion cata lyzed fluorination of aryl diazo sulfides in hydrogen fluonde-pyridine-toluene solvent [57] (equation 12) Electron withdrawing substituents such as acetyl give higher yields of aryl fluoride (71%) than electron donating groups (butyl 39%, methoxy, 2-14%), reductive dediazoniation competes with fluorination... 

Fluorinated olefins, such as chlorotritluoroethylene, hexafluoropropene, per-fluoroisobutylene, and hexafluorocyclobutene, react with silver trifluoroacetate in the presence of alkali metal fluondes to give perfluoroalkylsilver compounds [270] (equation 186)... 

Rearrangement of fluorine with concomitant ring opening takes place in fluorinated epoxides Hexafluoroacetone can be prepared easily from perfluo-ropropylene oxide by isomerization with a fluorinated catalyst like alumina pre treated with hydrogen fluoride [26, 27, 28] In ring-opening reactions of epoxides, the distribution of products, ketone versus acyl fluoride, depends on the catalyst [29] (equation 7) When cesium, potassium, or silver fluoride are used as catalysts, dimenc products also are formed [29]... 

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