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Pentafluorosulfur hypofluorite

Pentafluorosulfur hypofluorite is an inorganic compound with the chemical formula . In standard conditions it is a colorless gas. It is an oxyfluoride of sulfur, where sulfur is in the +6 oxidation state, with a fluorine atom attached to oxygen.

Synthesis

can be made by reacting thionyl fluoride with fluorine at 200 Ã‚°C with a silver difluoride catalyst.

(+ some )

The synthesis can also be performed from fluorine and thionyl fluoride or thionyl tetrafluoride using caesium fluoride as catalyst at room temperature.

Properties

The molecular shape has five fluorine and one oxygen atom arranged around a sulfur atom in an octahedral arrangement. Another fluorine atom is attached to the oxygen in almost a straight line with the S-O connection. So the molecular formula can also be written as . The average S-F distance is 1.53 ÃƒÂ…. The angles ∠FSF and ∠FSO are 90°.

The neat <sup>19</sup>F nuclear magnetic resonance spectrum of was reported using as internal standard. With this reference, a -131.5 ppm shift for the hypofluorite fluorine, a +1.75 ppm shift for F<sub>ax</sub> and a +3.64 ppm shift for the four F<sub>eq</sub> was observed. A 17.4 Hz <sup>19</sup>F-<sup>19</sup>F<sub>eq</sub> spin coupling (O-F to ) and a 155 Hz coupling constant was measured for <sup>19</sup>F<sub>ax</sub>-<sup>19</sup>F<sub>eq</sub> in OSF<sub>5</sub>. No coupling was observed between the hypofluorite and the F<sub>ax</sub>.

A neat (uncorrected) refined <sup>19</sup>F nuclear magnetic resonance spectrum of SOF<sub>6</sub> was recorded at -80°C. A first order quintet was observed for F-OSF<sub>5</sub> at 183.9 ppm with a <sup>3</sup>J(F,F<sub>eq</sub>) coupling of 17.5 Hz. A high order AB<sub>4</sub> system was observed for both the F<sub>eq</sub> and F<sub>ax</sub> of the OSF<sub>5</sub> moiety. The S–F<sub>ax</sub> shift is 52.2 ppm and the S–F<sub>eq</sub> is 50.3 ppm with a measured <sup>2</sup>J(F<sub>eq</sub>,F<sub>ax</sub>) of 153.5 Hz.

Reactions

Iodide is oxidised to iodine

Alkalis such as potassium hydroxide react

Alkenes react to add to a double bond, with on one carbon, and on the other.

.
.

boils at 15°C.

→ mixture of , , bis-(pentafluorosulfur) peroxide and bis-(pentafluorosulfur) oxide .

Thermal decomposition produces sulfur hexafluoride and oxygen.

.

Some reactions of result in fluorination of other molecules

.

References