Sulfur oxyhalides

As might be expected, there is a vast range of compounds containing sulfur halogen bonds (Figure 37), and they play an important role in synthetic sulfur chemistry. For convenience, they are divided by oxidation state. The sulfur oxyhalides are also dealt with in this section. 

Miller TM, Eriedman JF, Caples CM, Shuman NS, Van Doren JM, Bardaro MF Jr, Nguyen P, Zweiben C, Campbell M J, Viggiano AA. Electron attachment to sulfur oxyhalides SOE, SOClj, SOjEj, SOjCly and SO ECl attachment rate coefficients, 300-900 K. J Chem Phys. 2010 132 214302. 

The chemistry of the specific solvents discussed in this chapter illustrates the scope and utility of nonaqueous solvents. However, as a side note, several other nonaqueous solvents should at least be mentioned. For example, oxyhalides such as OSeCl2 and OPCl3 (described in the discussion of the coordination model earlier in this chapter) also have received a great deal of use as nonaqueous solvents. Another solvent that has been extensively investigated is sulfuric acid, which undergoes autoionization,... 

Tellurium Halides. Tellurium forms the dihalides TeCl and TeBi, but not Tel2. However, it forms tetrahalides with all four halogens. Tellurium decafluoride [53214-07-6] and hexafluoride can also be prepared. No monohalide, Te2X2, is believed to exist. Tellurium does not form well-defined oxyhalides as do sulfur and selenium. The tellurium halides show varying tendencies to form complexes and addition compounds with nitrogen compounds such as ammonia, pyridine, simple and substituted thioureas and anilines, and ethylenediamine, as well as sulfur trioxide and the chlorides of other elements. 

Lagowski, J. J., Ed., The Chemistry of Non-Aqueous Solvents, Academic, New York. This series contains detailed accounts of the purification, properties, and handling of some major solvents Vol. 2(1967), hydrogen halides, amides, and ammonia Vol. 3(1970), sulfur dioxide and acetic acid Vol. 4 (1976), tetramethylurea, cyclic carbonates, and sulfolane Vol. 5A (1978), tri-fluoroacetic acid, hafosuffuric acids, interhalogens, inorganic halides and oxyhalides. 

The sulfur analog, SPC13, and several mixed oxyhalides such as OPCI2F and OPCI2Br are known, but they are not widely used compounds. Oxyhalide compounds of arsenic, antimony, and bismuth are of much less importance than are those of phosphorus. 

Chemically, thionyl chloride can function as either a Lewis acid (sulfur is the acceptor atom) or a Lewis base (oxygen is the usual electron donor atom). It behaves in the same manner as other oxyhalides of sulfur and selenium with regard to hydrolysis, and the reaction can be shown as... 

Thousands of compounds of the actinide elements have been prepared, and the properties of some of the important binary compounds are summarized in Table 8 (13,17,18,22). The binary compounds with carbon, boron, nitrogen, silicon, and sulfur are not included these are of interest, however, because of their stability at high temperatures. A large number of ternary compounds, including numerous oxyhalides, and more complicated compounds have been synthesized and characterized. These include many intermediate (nonstoicliiometric) oxides, and besides the nitrates, sulfates, peroxides, and carbonates, compounds such as phosphates, arsenates, cyanides, cyanates, thiocyanates, selenocyanates, sulfites, selenates, selenites, teflurates, tellurites, selenides, and tellurides. 

A. Oxyhalides Containing One Atom of Sulfur per Molecule 1. Thionyl Fluoride, F2SO... 

The thionyl halides hydrolyze in water to give sulfur dioxide and HX. A common inorganic application of this reaction is for the preparation of anhydrous metal chlorides (although it can lead to difficulties for some metal chlorides). Industrially, thionyl chloride is used for the preparation of anhydrous metal halides and oxyhalides as well as in organic transformations, where it converts hydroxyl groups to chlorides. Over 50 000 tonnes a year are manufactured. 

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