Halides sulfur

Sulfur uses a wide range of oxidation numbers in its compounds with halogens, particularly with fluorine. The sulfur halides (also known as halosulfanes) that have been characterized are listed in Table 12.3. 

The product of the direct combination of sulfur with fluorine is the octahedral sulfur hexafluoride, SFg (12.7). Fluorine is the only halogen able to oxidize sulfur to the +6 state. Sulfur hexafluoride is chemically unreactive. It is both the most inert sulfur compound and the most inert covalent fluoride. This is in contrast to the lower fluorides and the other sulfur halides, which are reactive and, in particular, are readily hydrolysed. The reluctance of SFg to take part in chemical reaction is purely kinetic reactions such as the hydrolysis 

The lower fluorides, S2F2 and SF4, disproportionate readily into sulfur and SF6. The difluoro compound, S2F2, demonstrates unusual structural isomerism in that it can exist in two forms disulfur difluoride, F—S—S—F (12.8) and thiothionyl fluoride, S=SP2 (12.9). 

SF4 with its characteristic shape (Structure 12.10), is a useful selective fluorinating agent, which is capable, for example, of replacing the C=0 group in organic compounds by CF2 without affecting other functional groups. SF2 is unusual in that it exists both as the monomer and as a dimer (Structures 12.11 and 12.12, respectively). 

S2I2 is unstable, but can be prepared by shaking aqueous KI with S2CI2 in carbon disulfide it decomposes to Sg and other even-numbered ring allotropes. 

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Nitric acid, fuming Organic matter, nonmetals, most metals, ammonia, chlorosulfonic acid, chromium trioxide, cyanides, dichromates, hydrazines, hydrides, HCN, HI, hydrogen sulflde, sulfur dioxide, sulfur halides, sulfuric acid, flammable liquids and gases... 

Chloroethyldisulfides are obtained by electrophilic attack on the sulfur atom of thiiranes by sulfenyl halides (Scheme 39). Sulfur dichloride and disulfur dichloride react similarly to give more sulfur-rich derivatives di- and tri-sulfenyl halides, and tri- and tetra-sulfides (Scheme 42). A 1 1 ratio of sulfur halide to thiirane gives the di- or tri-sulfenyl halide a 2 1 ratio the tri- or tetra-sulfide. Thiirane 1-oxides are cleaved by sulfenyl halides to thiolsulfinates (Scheme 43) (74JAP7440461). 

Scheme 2.1 Preparation of S-N heterocycles from ammonia or ammonium salts and sulfur halides (i) reflux (ii) CCI4 or CH2CI2 (iii) CI2 (iv) Fe, Fig or Ph3Sb (v) S2CI2 (vi) KI...

The cyclic sulfur imides readily undergo condensation reactions in the presence of a base, e.g., pyridine. For example, the reaction of S7NH with sulfur halides, S Cla or SOCI2, produces the series (S7N)2Sx (x = 1, 2, 3, 5), or (S7N)2S0, respectively. The bicyclic compound S11N2 (6.6) is obtained by treatment of 1,3-S6(NH)2 with The reaction... 

A variety of routes is available for the preparation of metal-thionitrosyl complexes. The most common of these are (a) reaction of nitride complexes with a sulfur source, e.g., elemental sulfur, propylene sulfide or sulfur halides, (b) reaction of (NSC1)3 with transition-metal complexes, and (c) reaction of [SN]" salts with transition-metal complexes. An example of each of these approaches is given in Eq. 7.1,... 

The chemistry of 1,2,5-thiadiazole systems (RC)2N2S has been extensively investigated. " In addition to the condensation reactions of sulfur halides with 1,2-diaminobenzenes, this ring system is obtained in high yields by the reaction of S4N4 with acetylenes (Section 5.2.6). For example, the reaction of S4N4 with diphenylacetylene produces 3,4-diphenyl-1,2,5-thiadiazole in 87% yield. 

Schwefel-gold, n. gold sulfide, -grube,/. sulfur pit, sulfur mine, -halogen, n. sulfur halide. 

Although belonging to a slightly different class of reactions, the reaction of trifluoromethyl radicals with sulfur vapor has been shown to provide a route to trifluoromethyl polysulfide compounds (20). Instead of using sulfur halides, which undoubtedly would also give positive results, elemental sulfur (Ss) was vaporized and dissociated into atomic and polyatomic sulfur species. 

Gmelin Handbuch der Anorganischen Chemie, 8th ed.. Sulfur Halides, Springer, Berlin, 1978... 

Other examples of this synthetic strategy are known for example, a recent zirconium polymer by Illingsworth and Burke (8), who joined amine side groups of a zirconium bis(quadridentate Schiff-base) with an acid dianhydride to give amide linkages. Once again, caution is necesary, as Jones and Power (2) learned when they attempted to link metal bisO-diketonates) with sulfur halides that is, they obtained insoluble metal sulfides because the p-diketone complexes which they used were fairly labile and the insolubility drove the reactions to completion in the wrong direction. 

See Silver bromate Sulfur compounds Nitric acid Sulfur halides... 

See Dinitrogen pentaoxide Sulfur dichloride Nitric acid Sulfur halides Perchloryl fluoride Hydrocarbons, etc. 

IV. Sulfur Halides and Related Compounds of Divalent Sulfur... 

Sulfur furnaces, 23 771 heat of combustion from, 23 774 Sulfur halides, 23 640-647 Sulfur hexafluoride gas protection systems, 15 344... 

Beta carbonyl quaternary nitrogen Phosphorus or sulfur halides... 

Raw Fuel Cleaning - Removal of sulfur, halides, and ammonia to prevent fuel processor and fuel cell catalysts poisoning. 

Most abundant Hydrogen Carbon Sulfur Halides Inert gases... 

Elemental sulfur Sulfur cations Sulfur oxides Sulfur halide cations... 

Halogen abstraction from hypervalent sulfur halides has also been reported for the imidazol-2-ylidenes (IV) (Scheme 8.22). This reaction gives a nice example of the synthetic utihty of V-heterocyclic carbenes. Indeed, this adduct is the first structurally characterized derivative featuring the chlorosulfite ion (SO2CI ). ... 

The complexes of thiuram disulfide can be oxidized by an excess of halogens to products containing the bis(iminio)trithiolane dication (113).122 123 One of the sulfur atoms is removed as free sulfur or as sulfur halide. According to some reports the bis(iminio)tetrathiolane dication (114) also exists.124 In our investigations, however, we could not obtain any proof of this ion. The electrochemical literature about the oxidation of thiuram disulfide is also contradictory.125,126 Apart from the trithiolane ion a dithietane ion (115) is prepared by oxidation of dimethylformamide with bromine.127 As far as we know, no other disulfide can be oxidized to an analogous dication. 

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