Pentafluorosulfur hypofluorite

Thionyl tetrafluoride is a gas (m.p. —99.6°, b.p. —49°) which is hydrolyzed by water to sulfuryl fluoride and hydrogen fluoride. It may be handled in glass provided the system is dry, and it is readily identified by its infrared spectrum, which contains strong bands at 1383, 928, and 821 cm. .  

Pentafluorosulfur hypofluorite is also a gas, m.p. —86.0°, b.p. —35.1°. It is stable in glass, and can be easily identified by its infrared spectrum, which contains strong bands at 935 and 888 cm.. Pentafluorosulfur hypofluorite liberates 1 mole of iodine from an acidified potassium iodide solution per mole of hypofluorite added. It also reacts with water to liberate o.xygen. 

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Isopropyl hypochlorite, 1247 Methyl hypochlorite, 0434 Methyl hypofluorite, 0433 Nitryl hypochlorite, 4026 Pentafluoroselenium hypofluorite, 4368 Pentafluorosulfur hypofluorite, 4367... 

Nitrogen sulfur trifiuoride NSFs Pentafluorosulfur hypofluorite SFsOF Peroxydisulfuryl difluoride S20 F2... 1-Propanethiol CaHjSH 45 ... 

Fluorine perchlorate, 3970 Heptafluoroisopropyl hypofluorite, 1031 Heptafluoropropyl hypofluorite, 1057 Hypochlorous acid, 3989 Isopropyl hypochlorite, 1243 Methyl hypochlorite, 0433 Methyl hypofluorite, 0441 Nitryl hypochlorite, 4020 Pentafluoroselenium hypofluorite, 4362 Pentafluorosulfur hypofluorite, 4361... 

The very reactive yellow pentafluorosulfur hypofluorite is one of the few known hypofluorites it is obtained by the catalytic reaction... 

Thionyl tetrafluoride and pentafluorosulfur hypofluorite can be prepared by the fluorination of thionyl fluoride. The product distribution obtained upon fluorination appears to be dependent not only upon the reaction conditions, but on whether a source of fluoride ion is present. Fluorination of thionyl fluoride over a hot platinum gauze or in a Monel pressure reactor produces thionyl tetrafluoride, whereas fluorination in the presence of cesium fluoride or a silver fluoride catalyst jdelds pentafluorosulfur hypofluorite. The role of the fluoride ion in the fluorination has not been conclusively established however, the avail-... 

Although thionyl tetrafluoride and pentafluorosulfur hypofluorite can be prepared by fluorination in a flow reactor, the procedures described here are performed in a static system. This method offers several advantages. The metal equipment needed is commercially available, and the ability to closely control the stoichiometry of the reactions results in the formation of the products in high purity. However, the amount of material that can be prepared in one run is limited. Thionyl tetrafluoride may also be prepared in good yield by the oxidation of sulfur tetrafluoride. This method is also easy to carry out if the requisite high-pressure equipment is available. 

The procedures for the preparation of thionyl tetrafluoride and pentafluorosulfur hypofluorite are essentially the same, with one important difference the use of a catalyst. The apparatus employed in the preparations consists of several Monel pressure vessels (which have been prefluorinated at 150-200 ), a standard glass vacuum line equipped with several large calibrated storage bulbs (1- or 2-1.), a partial fractionation train, and several ball-joint connections on the main manifold. All the joints and stopcocks on the vacuum line are lubricated with Kel-F-90t grease, and all mercury manometers are covered with Kel-F-10 oil,t which has been well outgassed. The vacuum line is connected to a fluorine metering system and a water... 

Although the procedure described utilizes metal vessels for ease of treating the cesium fluoride and to avoid the formation of large amounts of silicon tetrafluoride, glass may be used. This procedure has been used for preparation of up to 0.015 mole of CF2(0F)2 at a time with the aid of liquid nitrogen to condense excess fluorine into the vessel. The method is analogous to that used in the preparation of pentafluorosulfur hypofluorite by the static, catalytic fluorination of thionyl fluoride in the presence of cesium fluoride. ... 

Pentafluorosulfur hypofluorite, F SOF, combines with CQ to give COFj, Clj and FgSOSFg according to [2193] ... 

In 1955 Dudley, working with Cady and Eggers, obtained pentafluorosulfur hypofluorite by the reaction of fluorine, in excess, with thionyl fluoride, or sulfur dioxide, at 200° in the presence of copper coated with fluorides of silver (78). It is probable that thionyl tetrafluoride is an intermediate in the process and that it combines with fluorine to give FjSOF. ... 

Pentafluorosulfur hypofluorite is a very reactive colorless gas having an odor resembling that of oxygen fluoride. It reacts with aqueous KI and aqueous KOH according to the equations ... 

Electron diffraction by pentafluorosulfur hypofluorite is consistent with the following structural features for the molecule rsr = 1.53 A, rop = 1.43 A, rso = 1.64 A, ZFSF = about 90°, ZSOF = about tetrahedral, somewhat greater than 103°, Z FSO (opposed F and 0 atoms) slightly different from 180°. The structure about the sulfur atom is essentially octahedral (61). 

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