Fluorine-sulfur compounds with nitrogen

System No 5 Fluorine Perfluorohaloorganic Compounds of Main Group Elements Supplementary, Vol 1 Compounds with Elements of Mom Groups I to 5 (EKcludtng Nitrogen) and with Sulfur (Partially)... 

The products of the electrochemical perfluorination of aromatic and heteroaromatic compounds are the corresponding perfluorinated cyclic and heterocyclic alkanes.28 and also per-fluorinated derivatives of the heteroaromatic compounds. Perfluorocyclohexane is the principal product from the electrochemical fluorination of benzene and fluorobenzene. Chloro derivatives of perfluorocyclohexane are produced from chlorobenzenes. Anisoles give fully saturated per-fluoro ethers, together with cleavage products. Extensive cleavage is observed in the fluorination of benzenethiols. Chloropyridines, fluorocarbons and sulfur hexafluoride or nitrogen trifluoride are characteristic byproducts from the above scries of reactions. 

Practice Problem 6.2 Name the compound with formula containing (a) two atoms of chlorine and three atoms of oxygen, (b) four atoms of sulfur and fom atoms of nitrogen, (c) two atoms of phosphorus and five atoms of sulfur, (d) two atoms of fluorine and one atom of sulfur. ... 

The reaction of amides with sulfur tetrafluoride or with carbonyl difluoride leads to fluorinated compounds with a nitrogen substituent at the difluoromethylene or trifluoromcthyl group and thus these reactions are not covered here. 

One of the most remarkable molecules is thiazyl trifluoride, NSF, (Fig. 18.7). This compound is very stable. It does not react with ammonia at room temperature, with hydrogen chloride even when heated, or with metallic sodium at temperatures below 400 °C. The S—N bond, 141,6 pm. is the shortest known between these two elements. The F.SF bond angles of 94° are compatible with approximate sp bonding and the presence of an. vp hybrid (t bond and two p-d n bonds between the sulfur and the nitrogen. The contraction of the d orbitals by the inductive effect of the fluorine atoms presumably permits effective overlap and rr-bond formation. The alternative explanation would require a double dative bond from the sulfur atom, extremely unlikely in view of the positive character of the sulfur atom. 

BENSULFOID (7704-34-9) Combustible solid (flash point 405°F/207°C). Finely divided dry materia forms explosive mixture with air. The vapor reacts violently with lithium carbide. Reacts violently with many substances, including strong oxidizers, aluminum powders, boron, bromine pentafluoride, bromine trifluoride, calcium hypochlorite, carbides, cesium, chlorates, chlorine dioxide, chlorine trifluoride, chromic acid, chromyl chloride, dichlorine oxide, diethylzinc, fluorine, halogen compounds, hexalithium disilicide, lampblack, lead chlorite, lead dioxide, lithium, powdered nickel, nickel catalysis, red phosphorus, phosphorus trioxide, potassium, potassium chlorite, potassium iodate, potassium peroxoferrate, rubidium acetylide, ruthenium tetraoxide, sodium, sodium chlorite, sodium peroxide, tin, uranium, zinc, zinc(II) nitrate, hexahydrate. Forms heat-, friction-, impact-, and shock-sensitive explosive or pyrophoric mixtures with ammonia, ammonium nitrate, barium bromate, bromates, calcium carbide, charcoal, hydrocarbons, iodates, iodine pentafluoride, iodine penloxide, iron, lead chromate, mercurous oxide, mercury nitrate, mercury oxide, nitryl fluoride, nitrogen dioxide, inorganic perchlorates, potassium bromate, potassium nitride, potassium perchlorate, silver nitrate, sodium hydride, sulfur dichloride. Incompatible with barium carbide, calcium, calcium carbide, calcium phosphide, chromates, chromic acid, chromic... 

The large number of fluorine-containing compounds of sulfur results from the ability of sulfur to form strong covalent bonds with itself or with fluorine, oxygen, carbon, chlorine, phosphorus, and nitrogen. It is also important that sulfur may have coordination numbers of 2, 3, 4, 5, and 6. Formulas of a few compounds which illustrate the versatility of sulfur are ... 

In the first section of this chapter some of the properties of the elements hydrogen, carbon, nitrogen, phosphorus, arsenic, antimony, bismuth, oxygen, sulfur, selenium, tellurium, fluorine, chlorine, bromine, and iodine are described. The following sections are devoted to some of their compounds with one another, especially the single-bonded normal-valence compounds. Compounds of nonmetals with oxygen are discussed in the following chapter. 

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