Fluorine fluoridation with

Graphite reacts with alkali metals, for example potassium, to form compounds which are non-stoichiometric but which all have limiting compositions (for example K C) in these, the alkaU metal atoms are intercalated between the layers of carbon atoms. In the preparation of fluorine by electrolysis of a molten fluoride with graphite electrodes the solid compound (CF) polycarbon fluoride is formed, with fluorine on each carbon atom, causing puckering of the rings. 

Hydrogen fluoride is the most important compound of fluorine. It is prepared in the laboratory, and on the large scale, by the reaction of calcium fluoride with concentrated sulphuric acid. ... 

On the average, one part of radon is present ot 1 x IO21 part of air. At ordinary temperatures radon is a colorless gas when cooled below the freezing point, radon exhibits a brilliant phosphorescence which becomes yellow as the temperature is lowered and orange-red at the temperature of liquid air. It has been reported that fluorine reacts with radon, forming a fluoride. Radon clathrates have also been reported. 

Fluorine reacts with ammonia in the presence of ammonium acid fluoride to give nitrogen trifluoride, NF. This compound can be used as a fluorine source in the high power hydrogen fluoride—deuterium fluoride (HF/DF) chemical lasers and in the production of microelectronic siUcon-based components. 

Fluorinated ether-containing dicarboxyhc acids have been prepared by direct fluorination of the corresponding hydrocarbon (17), photooxidation of tetrafluoroethylene, or by fluoride ion-cataly2ed reaction of a diacid fluoride such as oxalyl or tetrafluorosuccinyl fluorides with hexafluoropropylene oxide (46,47). Equation 8 shows the reaction of oxalyl fluoride with HEPO. A difunctional ether-containing acid fluoride derived from HEPO contains regular repeat units of perfluoroisopropoxy group and is terminated by two alpha-branched carboxylates. 

Fluorine. Fluoride is present in the bones and teeth in very small quantities. Human ingestion is from 0.7—3.4 mg/d from food and water. Evidence for the essentiaUty of fluorine was obtained by maintaining rats on a duoride-free diet, resulting in decreased growth rate, decreased fertihty, and anemia. These impairments were remedied by supplementing the diets with duoride (81). Similar effects have been reported in goats (82). 

Fluoroformyl peroxide [692-74-0] (20, R = R = F), has been prepared by the reaction of carbon monoxide, fluorine, and oxygen or by the photolytic reaction of oxalyl fluoride with oxygen (187). 

Fluorides. Tantalum pentafluoride [7783-71-3] TaF, (mp = 96.8° C, bp = 229.5° C) is used in petrochemistry as an isomerization and alkalation catalyst. In addition, the fluoride can be utilized as a fluorination catalyst for the production of fluorinated hydrocarbons. The pentafluoride is produced by the direct fluorination of tantalum metal or by reacting anhydrous hydrogen fluoride with the corresponding pentoxide or oxychloride in the presence of a suitable dehydrating agent (71). The ability of TaF to act as a fluoride ion acceptor in anhydrous HF has been used in the preparation of salts of the AsH, H S, and PH ions (72). The oxyfluorides TaOF [20263-47-2] and Ta02F [13597-27-8] do not find any industrial appHcation. 

Cadmium Fluoride. Elemental fluorine reacts with cadmium metal as well as the oxide, sulfide, and chloride to give CdF2 [7790-79-6]. Alternatively, treatment of CdCO with 40% HF yields a solution of CdF2, which may be evaporated to recover efflorescent crystals of the dihydrate. CdF2 has been used in phosphors, glass manufacture, nuclear reactor controls, and electric bmshes and in 1991 sold as a pure electronic grade (99.99%) at l/g. 

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. ... 

Stenc effects are presumably also responsible for the surprising formation of a chlorinated product from reaction of a hindered fluorinated olefin with potassium fluoride and iodine chloride [U6] (equation 18). 

Polyethylene glycol (molecular weight, 300-6(W) can aid in the displacement of activated halogen by fluorine. Propionyl chloride is converted to propionyl fluoride with potassium fluoride and polyethylene glycol in acetonitrile [63] Treatment of benzyl chloride with a mixture of potassium fluoride and potassium iodide for 5 h in acetonitrile containing polyethylene glycol 200 gives benzyl fluoride in 62% yield [64],... 

Fluorides with fluorine-phosphorus bonds also react with Lewis acids tert-Butylpentafluorocyclotriphosphazenes are arylated in the presence of aluminum chlonde [26] (equation 18)... 

Sulfur tetrafluoride, SF4, though extremely reactive (and valuable) as a selective fluorinating agent, is much more stable than the lower fluorides. It is formed, together with SFg, when a cooled film of sulfur is reacted with F2, but is best prepared by fluorinating SCI2 with NaF in warm acetonitrile solution ... 

Fluorine is the most reactive of all elements, in part because of the weakness of the F—F bond (B.E. F—F = 153 kj/mol), but mostly because it is such a powerful oxidizing agent (E ed = +2.889 V). Fluorine combines with every element in the periodic table except He and Ne. With a few metals, it forms a surface film of metal fluoride, which adheres tightly enough to prevent further reaction. This is the case with nickel, where the product is NiF2. Fluorine gas is ordinarily stored in containers made of a nickel alloy, such as stainless steel (Fe, Cr, Ni) or Monel (Ni, Cu). Fluorine also reacts with many compounds including water, which is oxidized to a mixture of 02> 03> H202, and OF2. 

Consider the fluorides of the second-row elements. There is a continuous change in ionic character of the bonds fluorine forms with the elements F, O, N, C, B, Be, and Li. The ionic character increases as the difference in ionization energies increases (see Table 16-11). This ionic character results in an electric dipole in each bond. The molecular dipole will be determined by the sum of the dipoles of all of the bonds, taking into account the geometry of the molecule. Since the properties of the molecule are strongly influenced by the molecular dipole, we shall investigate how it is determined by the molecular architecture and the ionic character of the individual bonds. For this study we shall begin at the left side of the periodic table. 

Noyori and coworkers found that tetrafluorosilane or trimethylsilyl tri-flate catalyzes the condensation of appropriately protected glycopyranosyl fluorides with trimethylsilyl ethers or alcohols. The strong affinity of silicon for fluorine was considered to be the driving force for this reaction. In the case of Sip4, attack of a nucleophile on the glycosyl cation-SiFj ion-pair intermediate was anticipated. Thus, condensation of 2,3,4,6-tetra-O-benzyl-a- and - -D-glucopyranosyl fluorides (47a and 47fi) with methyl... 

Figure 38 shows three fluorine-19 spectra a potassium fluoride in D20 b trifluoroacetic acid and c p-fluorophenol in CDC13 (with expansion). Line-widths are small 1.9 Hz in spectrum a, 1.3 Hz in spectrum b. The computer printout in c shows that what is apparently one single line is in fact a multiplet, and the expansion shows a complex multiplet due to coupling of the fluorine nucleus with the two protons ortho and the two protons meta to it. 

Another remarkable example of a mercuracarborand halide adduct has been obtained by reaction of the octamethyl tetranuclear derivative 165 with [NMe4]F. This reaction affords complex [165-F]- in which the fluoride is coordinated to the four mercury centers in an approximate square-planar arrangement (Equation (57)). The Hg-F distances, which range from 2.56 to 2.65 A, are slightly longer than those found in [163-/i2-F]2. The 9Hg NMR resonance of the complex indicates coupling to the fluorine atom with 1Jug-F = 698 Hz.215... 

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