Pentafluorosulfur hypofluorite

Pentafluorosulfur hypofluorite
Names
	IUPAC name Pentafluorosulfur hypofluorite
Identifiers
3D model (JSmol)	Interactive image;
	SMILES S(F)(F)(F)(F)(F)OF;
Properties
Chemical formula	SOF6
Appearance	colorless 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]
Solubility in water	reaction in water
log P	6.03633-420.35/T-78360/T²[1]
Related compounds
Related oxohalides	Thionyl tetrafluoride; Thionyl fluoride,; sulfonyl fluoride
Related compounds	sulfuryl fluoride; sulfur hexafluoride; pentafluorooxosulfuric acid; bis-(pentafluorosulfur) oxide; bis-(pentafluorosulfur) peroxide; bis-(pentafluorosulfur) trioxide
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
	Infobox references

Pentafluorosulfur hypofluorite is an oxyfluoride of sulfur in the +6 oxidation state, with a fluorine atom attached to oxygen. The formula is SOF₆. In standard conditions it is a gas.^[1]

Synthesis

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

SOF₂ + 2F₂ → 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 SF₅OF. 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

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

Alkalis such as potassium hydroxide react

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

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

C₂H₄ + SOF₆ → FH₂CCH₂OSF₅.^[4]

C₂F₄ + SOF₆ → CF₃CF₂OSF₅.^[4] C₂SOF₁₀ boils at 15°C

SOF₆ + ClCH=CH₂ → FClCH-CH₂-O-SF₅^[5]

SOF₆ + FCH=CH₂ → F₂CH-CH₂-O-SF₅^[5]

SOF₆ + F₂C=CH₂ → F₃CH-CH₂-O-SF₅^[5]

SOF₆ + SOF₄ → mixture of SF₆, SOF₄, bis-(pentafluorosulfur) peroxide F₅SOOSF₅ and bis-(pentafluorosulfur) oxide F₅SOSF₅.^[4]

Thermal decomposition produces thionyl tetrafluoride and oxygen.

2SOF₆ heat over 210° → 2SF₆ + O₂.^[4]

Some reactions of SOF₆ result in fluorination of other molecules

SOF₆ + CO → F₂CO + SOF₄.^[4]

SOF₆ + F₂CO → SF₅OOCF₃^[6]

SOF₆ + SO₃ → F₅SOOSO₂F^[6]

SOF₆ + N₂F₄ → F₅SONF₂^[6]

3SOF₆ + Br₂ → 2BrF₃ + 3SOF₄^[6]

5SOF₆ + I₂ → 2IF₅ + 5SOF₄^[6]

PF₃ + SOF₆ → PF₅ + SOF₄^[6]

NO₂ + SOF₆ → 2NO₂F^[6]

References

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. doi:10.1021/ja01589a013.
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. doi:10.1021/ja01529a009.
↑ Emsley, J. W.; Feeney, J.; Sutcliffe, L. H. High Resolution Nuclear Magnetic Resonance Spectroscopy. Elsevier. p. 949. ISBN 9781483184081.
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.
1 2 3 Williamson, Stanley M. (1963). "On the Reaction of Pentafluorosulfur Hypofluorite with Unsymmetrical Two-Carbon Alkenes". Inorganic Chemistry. 2 (2): 421. doi:10.1021/ic50006a050.
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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[dud-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. doi:10.1021/ja01589a013.

[craw-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. doi:10.1021/ja01529a009.

[3] Emsley, J. W.; Feeney, J.; Sutcliffe, L. H. High Resolution Nuclear Magnetic Resonance Spectroscopy. Elsevier. p. 949. ISBN 9781483184081.

[will-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.

[will2-5] 1 2 3 Williamson, Stanley M. (1963). "On the Reaction of Pentafluorosulfur Hypofluorite with Unsymmetrical Two-Carbon Alkenes". Inorganic Chemistry. 2 (2): 421. doi:10.1021/ic50006a050.

[tat-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.