Fluorine complex with ammonia

Very recently, various DHB complexes were analyzed [39].12 The complexes of ammonia and hydronium ions were included in this analysis, in addition to the complexes with acetylene and methane, and their derivatives. Generally, in such complexes, lithium hydride and berylium hydride (and its fluorine derivative) act as the Lewis bases (proton acceptors) while hydronium ion, ammonia ion, methane, acetylene, and their simple derivatives act as the proton donors. Therefore, it was possible to investigate the wide spectrum of DHB interactions, starting from those that possess the covalent character and extending to the systems that are difficult to classify as DHBs (since they rather possess the characteristics of the van der Waals interactions). Figure 12.8 displays the relationship between H—H distance and the electron density at H—H BCP.13 One can observe the H—H distances close to 1 A, (as for the covalent bond lengths) and also the distances of about 2.2—2.5 A, typical for the van der Waals contacts. This also holds for the pc-values - of the order of 0.1 a.u. as for the covalent bonds and much smaller values as for the HBs and weaker interactions. 

Two fluorinations which produce HNF2 directly are (1) the direct fluorination of urea at 0° C. and subsequent distillation of the corrosive liquid produced, which gives up to 15% yields of HNF2 as reported by Lawton and Weber (14), and (2) the direct fluorination of excess ammonia with a packed reactor which gives complex mixture containing small amounts of HNF2 as reported by Morrow (27) and coworkers. 

Perchlorates are powerful oxidizing substances. These compounds explode when mixed with combustible, organic, or other easily oxidizable compounds and subjected to heat or friction. Perchlorates explode violently at ambient temperatures when mixed with mineral acids, finely divided metals, phosphorus, trimethylphosphite, ammonia, or ethylenediamine. Explosions may occur when perchlorates are mixed with sulfur, or hydride of calcium, strontium, or barium and are subjected to impact or ground in a mortar. Perchlorates react with fluorine to form fluorine perchlorate, an unstable gas that explodes spontaneously. Heating perchlorates to about 200°C (392°F) with charcoal or hydrocarbons can produce violent explosions. Metal perchlorates from complexes with many organic solvents, which include benzene, toluene, xylenes, aniline, diozane, pyridine, and acetonitrile. These complexes are unstable and explode when dry. Many metal perchlorates explode spontaneously when recrystaUized from ethanol. Saturated solution of lead perchlorate in mathanol is shock sensitive. 

Equations (141) and (142) describe the equilibrium between the hydrolysis of complex fluoride acids (shift to the right) and the fluorination of hydroxides (shift to the left). Near complete precipitation of hydroxides can be achieved by applying an excessive amount of ammonia. Typically, precipitation is performed by adding ammonia solution up to pH = 8-9. However, the precipitate that separates from the mother solution can be contaminated with as much as 20% wt. fluorine [490]. Analysis of niobium hydroxides obtained under different precipitation conditions showed that the most important parameter affecting the fluorine content of the resultant hydroxide is the amount of ammonia added [490]. Sheka et al. [491] found that increasing the pH to 9.6 toward the end of the precipitation process leads to a significant reduction in fluorine content of the niobium hydroxide. 

The comparatively simple method of preparation of tetrakis (trifluorophos-phine)nickel-(0) encouraged some scouting experiments on its still unexplored chemistry. Whereas the compound is hydrolytically remarkably stable, it was found to react readily with amines and ammonia with complete aminolysis of the phosphorus-fluorine bonds. Very typical of tetrakis(trifluorophosphine) nickel-(0) and similar fluorophosphine and chlorophosphine complexes of zerovalent nickel is the rapid decomposition with precipitation of elemental nickel by aqueous alkali hydroxide. 

It was decided to study the system tetrakis (trifluorophosphine) nickel- (0) -ammonia (23) in some detail a smooth reaction was observed when the complex, condensed on excess ammonia at liquid air temperature, was allowed to warm up gradually. Precipitation of colorless crystals, identified as ammonium fluoride in almost stoichiometric amount, based on complete ammonolysis of the phosphorus-fluorine bonds, was observed at temperatures as low as —90° to —80°. Removal of the ammonium fluoride by filtration at temperatures not higher than —50°, and subsequent slow evaporation of the ammonia from the filtrate invariably led to a brown-yellow solid, although a colorless, crystalline material was formed initially. The product was decomposed almost instantaneously by water with precipitation of elemental nickel. Analysis of the hydrolyzate obtained in aqueous hydrochloric acid revealed a nickel-phosphorus-nitrogen atom ratio close to 1 4 4, corresponding to an apparently polymeric condensation product. 

Trihalides of nitrogen with fluorine and chlorine can be isolated, but with bromine and iodine only the ammonia complexes, NBr3(NHg)g and Nl3(NH3), are known. 

Perfluoroalkanesulfonamides have been claimed as intermediates for the synthesis of fluorinated surfactants. Their synthesis by reaction of the corresponding perfluoroalkanesulfonyl fluoride (or chloride) with liquid ammonia is prototypical for the synthesis of alkylated perfluoroalkane-sulfonamide surfactants. This reaction initially forms a complex ammonium salt as shown in Scheme 18.2. The desired amide is obtained by dissolving the crude product in dioxane and... 

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