Sulfur chloride pentafluoride

Submitted by F. Nyman, H. L. Roberts, and T. Seaton Checked by John W. GEOROEf 

The first reported preparations of sulfur chloride penta-fluoride involved the fluorination of sulfur(II) chloride, the chlorination of disulfur decafluoride, and the electrolysis of sulfur(II) chloride-hydrogen fluoride mixtures. Newer methods utilize the reaction between chlorine monofluoride and sulfur(IV) fluoride or the reaction between chlorine, cesium fluoride, and sulfur(IV) fluoride. The directions described here for the reaction between chlorine monofluoride and sulfur(IV) fluoride are for the preparation of substantial quantities if only a 1- or 2-g. sample is required, the modifications described in the last paragraph of the Procedure section may be employed or a batch pro- 

Caution. The reagents and products are extremely toxic, particularly sulfur chloride pentafluoride and disulfur decafluoride. 

The starting materials, chlorine, chlorine trifluoride, and sulfur(IV) fluoride can be purchased in cylinders and can be used as received. 

The required apparatus (Fig. 5) consists of two flowmeters suitable for use with easily hydrolyzed fluorine compounds, one capillary or Rotameter flowmeter for chlorine, two nickel tubes 4 ft. long X 2 in., and two tube furnaces capable of heating the tubes to 400 5°. Metal tubing is 

Submitted by CARL J. SCHACK, RICHARD D. WILSON, and MICHAEL G. WARNERt Checked by A. WATERFELDf 

Sulfur chloride pentafluoride has utility in the preparation of numerous inorganic and organic derivatives. A procedure for its synthesis has appeared previously in this series. This method involved the in situ generation of CIF by a hot flow tube reaction followed by a second hot flow tube reaction of the CIF and SF4 to furnish SCIF,. These reactions are time consuming to set up and sometimes difflcult to master. A far simpler synthesis is the reaction of SF4 and CIF at ambient temperature in the presence of CsF. The reaction proceeds rapidly and in high yield with a minimum of by-product formation, thus allowing easy separation of the products. 

Inorganic Syntheses, Volume 24 Edited by Jean ne M. Shreeve 1986 by Inorganic Syntheses, Inc. 

Shreeve, in Sulfur in Organic and Inorganic Chemistry, Vol. 4, A. Senning (ed.), Marcel 

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Tris(2,4-pentanedionato)molybdenum(III), synthesis 39 Potassium tetraoxalatouranate(IV), synthesis 40 Sulfur chloride pentafluoride, synthesis 41 Trifluoromethyl hypofluorite, synthesis 42 Ammonium perrhcnate, synthesis 43... 

Sulfur chloride pentafluoride is a colorless, highly toxic gas. It condenses to a colorless liquid at —19.1° and freezes to a white solid at —64°, Its vapor pressure over the range —60 to —20° may be calculated from the equation ... 

Sulfur chloride pentafluoride can be reduced photochemi-cally to the very toxic S2F10 and can be o.xidized photo-chemically to a mixture of SFsOSFs and SFsOOSFg. With olefins, it reacts to form a variety of organic sulfur pentafluorides. The ultraviolet irradiation of a mixture of sulfur chloride pentafluoride and dinitrogen tetrafluoride yields SFgNFj. ... 

ClFsS, Sulfur chloride pentafluoride, 24 8 CIFsTe, Tellurium chloride pentafluoride, 24 31... 

Ghloro-l-sulfur pentafluorides from ethylene derivatives and sulfur chloride pentafluoride... 

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