Pentafluorosulfur hypofluorite

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Pentafluorosulfur hypofluorite
Pentafluorosulfur hypofluorite.png
Names
IUPAC name
Pentafluorosulfur hypofluorite
Other names
  • Sulfur fluoride hypofluorite
  • Thionyl fluoride hypofluorite
Identifiers
3D model (JSmol)
PubChem CID
  • InChI=1S/F6OS/c1-7-8(2,3,4,5)6
    Key: DGQBNDRZRZYTER-UHFFFAOYSA-N
  • S(F)(F)(F)(F)(F)OF
Properties
SOF6
Molar mass 162.05 g·mol−1
AppearanceColorless gas
Density 1.947 at -47.2 °C [1]
Melting point −86 °C (−123 °F; 187 K) [1]
Boiling point −35.1 °C (−31.2 °F; 238.1 K) [1]
Reacts with water
log P 6.03633-420.35/T-78360/T2 [1]
Related compounds
Related oxohalides
Related compounds
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Pentafluorosulfur hypofluorite is an inorganic compound with the chemical formula S O F 6. 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. [1]

Contents

Synthesis

SOF6 can be made by reacting thionyl fluoride with fluorine at 200 °C with a silver difluoride catalyst. [2]

SOF2 + 2 F2 → SOF6 (+ some SOF4)

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 SF5−OF. The average S-F distance is 1.53 Å. The angles ∠FSF and ∠FSO are 90°. [2]

The 19F nuclear magnetic resonance spectrum of SOF6 compared to SF6 has a -131.5 ppm shift for the hypofluorite fluorine, and 1.75 ppm for the opposite F. The other four fluorine atoms have a shift of 3.64 ppm. Spin coupling of O-F to SF4 is 17.4 Hz, between SF4 and opposite (apex) SF 155 Hz, and between apex and hypofluorite it is 0.0. [3]

Reactions

Iodide is oxidised to iodine

SOF6 + 2 I− + H2O → SO2F2 + I2 + 2 HF + 2 F−

Alkalis such as potassium hydroxide react

2 SOF6 + 12 OH− → O2 + 10 F− + 5 H2O + 2 SO3F−

Alkenes react to add to a double bond, with −OSF5 on one carbon, and −F on the other.

C2H4 + SOF6 → FH2C−CH2−O−SF5. [4]
C2F4 + SOF6 → CF3−CF2−O−SF5. [4]

CF3−CF2−O−SF5 boils at 15°C.

SOF6 + ClCH=CH2 → FClCH−CH2−O−SF5 [5]
SOF6 + FCH=CH2 → F2CH−CH2−O−SF5 [5]
SOF6 + F2C=CH2 → F3C−CH2−O−SF5 [5]
SOF6 + SOF4 → mixture of SF6, SOF4, bis-(pentafluorosulfur) peroxide F5S−O−O−SF5 and bis-(pentafluorosulfur) oxide F5S−O−SF5. [4]

Thermal decomposition produces sulfur hexafluoride and oxygen.

2 SOF6 + heat over 210° → 2 SF6 + O2. [4]

Some reactions of SOF6 result in fluorination of other molecules

SOF6 + CO → F2CO + SOF4. [4]
SOF6 + F2CO → SF5−O−O−CF3 [6]
SOF6 + SO3 → F5S−O−O−SO2F [6]
SOF6 + N2F4 → F5S−O−NF2 [6]
3 SOF6 + Br2 → 2 BrF3 + 3 SOF4 [6]
5 SOF6 + I2 → 2 IF5 + 5 SOF4 [6]
PF3 + SOF6 → PF5 + SOF4 [6]
NO2 + SOF6 → 2 NO2F [6]

References

  1. 1 2 3 4 5 Dudley, F. B.; Cady, G. H.; Eggers, D. F. (April 1956). "Pentafluorosulfur Hypofluorite and Thionyl Tetrafluoride". Journal of the American Chemical Society. 78 (8): 1553–1557. Bibcode:1956JAChS..78.1553D. doi:10.1021/ja01589a013.
  2. 1 2 Crawford, Roger A.; Dudley, Frank B.; Hedberg, Kenneth (October 1959). "A Verification of the Molecular Structure of Pentafluorosulfur Hypofluorite (SF5OF) by Electron Diffraction". Journal of the American Chemical Society. 81 (20): 5287–5288. Bibcode:1959JAChS..81.5287C. doi:10.1021/ja01529a009.
  3. ↑ Emsley, J. W.; Feeney, J.; Sutcliffe, L. H. (22 October 2013). High Resolution Nuclear Magnetic Resonance Spectroscopy. Elsevier. p. 949. ISBN   9781483184081.
  4. 1 2 3 4 5 Williamson, Stanley M.; Cady, George H. (August 1962). "Reactions of Pentafluorosulfur Hypofluorite". Inorganic Chemistry. 1 (3): 673–677. doi:10.1021/ic50003a044.
  5. 1 2 3 Williamson, Stanley M. (1963). "On the Reaction of Pentafluorosulfur Hypofluorite with Unsymmetrical Two-Carbon Alkenes". Inorganic Chemistry. 2 (2): 421–422. doi:10.1021/ic50006a050.
  6. 1 2 3 4 5 6 7 Tattershall, B.W.; Cady, George H. (December 1967). "Reactions of pentafluorosulphur hypofluorite (SF5OF) with Cl2, Br2, I2, NO2, and PF3". Journal of Inorganic and Nuclear Chemistry. 29 (12): 3003–3005. doi:10.1016/0022-1902(67)80134-9.
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