Sulphur-Oxygen-Halogen Compounds

Sulphur-Oxygen-Halogen Compounds.—Thionyl fluoride has been shown76 to react with Cl2F+AsF6 at —78 °C to give OSCIFz AsFe in ca. 85% yield  

Several new, as well as a large number of known, fluorosulphate-containing molecules have been synthesized79 via hydrogen radical abstraction with S206F2  

2XeF+AsF6- + K+S03F - (FXe)2S03F+AsF6 + AsF6- (26) 

Sulphuryl fluoride dissolves rapidly in HzO, and may be removed from solution by dynamic vacuum.85 Hydrolysis is slow in water but rapid in basic solutions, the net reaction being  

The reaction is considered to be a nucleophilic displacement of fluoride in which the controlling process is  

Three different methods for the preparation of peroxydisulphuryl difluoride have been described. In the first preparation, S2O6F2 was prepared by mixing HSO3F and [AsFe] at low temperatures. The latter compound was prepared photochemically from AsF, O2, and F2. The second preparation involves the quantitative reaction of CrFj with SO3 according to the equation  

Pure S2O6F2 may be removed from the reaction mixture at -22 °C, and the other reaction product, Cr(S03p)3, which had not been isolated previously, was also studied in some detail. The third paper describes the preparation of 

FSO4F is a strong oxidizing agent and caused explosions when being warmed rapidly from —196 to —20°C, and when it reacted with organic matter. 

Brown and G. L. Card, Inorg. Nuclear Chem. Letters, 1975, 11, 19. 

Specific conductance, i.r., and H n.m.r. spectra of HN(S02CI)2 have been reported. It behaves as a 1 1 electrolyte in PhN02 and forms a 1 1 adduct with pyridine i.r. spectra of the latter indicate the presence of pyH and [N(S02C1)2] ions. Further data was obtained to support the autoionization  

Raman spectroscopy. All eleven fundamental vibrations expected for a pseudo-octahedral anion (18) of symmetry Cit, were observed and assigned. 

A modified valence force field was computed for the ion SF O , which showed a value of the SO stretching force constant lower than those found for S=0 double bonds and suggested an SO bond order of about 1.5. Likewise, low values were found for S—F stretching force constants, thus indicating significant ionic contributions to the SF bonds in SFjO . These results were therefore interpreted in terms of the resonance structures (19) and (20). 

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For compounds containing carbon, hydrogen, oxygen, nitrogen halogens and sulphur. If the compound to be analysed contains sulphur in addition to the elements considered above, then oxides of sulphur will be formed, and a new... 

Concentrated sulphuric acid. The paraffin hydrocarbons, cych-paraffins, the less readily sulphonated aromatic hydrocarbons (benzene, toluene, xylenes, etc.) and their halogen derivatives, and the diaryl ethers are generally insoluble in cold concentrated sulphuric acid. Unsaturated hydrocarbons, certain polyalkylated aromatic hydrocarbons (such as mesitylene) and most oxygen-containing compounds are soluble in the cold acid. 

The effect of a particular element on the odour of its compound seems also to lend support to the residual affinity theory, for it is only the elements which possess residual affinity in certain of their compounds, which function as osmophores. Oxygen, nitrogen, sulphur, phosphorous, halogens, arsenic, antimony, bismuth, etc., whose valencies vary under certain conditions are powerfully osmophoric whereas carbon, hydrogen, and many others which have a constant valency are practically non-osmophoric, and it is very instructive to note that the element is osmophoric when it is not employing its full number of valencies and therefore has free affinity. 

C18 Reversed phases are not necessarily limited to polycyclic and halogenated (or nitrated) hydrocarbons, but can be used for a number of oxygen-, nitrogen- and sulphur- containing heterocyclic compounds in a similar way to that used in reversed-phase chromatography. In this context, ref. 185 describes the separation of compounds of this category. A plethora of similar separations can be found in the Section devoted... 

Volatilization is usually utilized for separating individual trace elements from the sample before the determination. The methods based on volatilization are concerned mainly with non-metallic and amphoteric elements which have high vapour pressure in the elemental form (e.g., chlorine, bromine, sulphur), or in compounds with halogen, hydrogen, or oxygen. Other volatilization methods exist for the separation of certain elements, such as the distillation of boron as methyl borate. 

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