Pentafluorosulfur hypofluorite

Last updated
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
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
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).

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]

Contents

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

Iodide is oxidised to iodine

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 → F3C-CH2-O-SF5 [5]
SOF6 + SOF4 → mixture of SF6, SOF4, bis-(pentafluorosulfur) peroxide F5SOOSF5 and bis-(pentafluorosulfur) oxide F5SOSF5. [4]

Thermal decomposition produces sulfur hexafluoride 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 + Br22BrF3 + 3SOF4 [6]
5SOF6 + I2 → 2IF5 + 5SOF4 [6]
PF3 + SOF6PF5 + SOF4 [6]
NO2 + SOF6 → 2NO2F [6]

Related Research Articles

In chemistry, halogenation is a chemical reaction that entails the introduction of one or more halogens into a compound. Halide-containing compounds are pervasive, making this type of transformation important, e.g. in the production of polymers, drugs. This kind of conversion is in fact so common that a comprehensive overview is challenging. This article mainly deals with halogenation using elemental halogens (F2, Cl2, Br2, I2). Halides are also commonly introduced using salts of the halides and halogen acids. Many specialized reagents exist for and introducing halogens into diverse substrates, e.g. thionyl chloride.

In chemistry, a hypervalent molecule is a molecule that contains one or more main group elements apparently bearing more than eight electrons in their valence shells. Phosphorus pentachloride, sulfur hexafluoride, chlorine trifluoride, the chlorite ion, and the triiodide ion are examples of hypervalent molecules.

<span class="mw-page-title-main">Thionyl chloride</span> Inorganic compound (SOCl2)

Thionyl chloride is an inorganic compound with the chemical formula SOCl2. It is a moderately volatile, colourless liquid with an unpleasant acrid odour. Thionyl chloride is primarily used as a chlorinating reagent, with approximately 45,000 tonnes per year being produced during the early 1990s, but is occasionally also used as a solvent. It is toxic, reacts with water, and is also listed under the Chemical Weapons Convention as it may be used for the production of chemical weapons.

Dioxygen difluoride is a compound of fluorine and oxygen with the molecular formula O2F2. It can exist as an orange-colored solid which melts into a red liquid at −163 °C (110 K). It is an extremely strong oxidant and decomposes into oxygen and fluorine even at −160 °C (113 K) at a rate of 4% per dayits lifetime at room temperature is thus extremely short. Dioxygen difluoride reacts vigorously with nearly every chemical it encounters (including ordinary ice) leading to its onomatopoeic nickname FOOF (a play on its chemical structure and its explosive tendencies).

<span class="mw-page-title-main">Thionyl fluoride</span> Chemical compound

Thionyl fluoride is the inorganic compound with the formula SOF
2
. This colourless gas is mainly of theoretical interest, but it is a product of the degradation of sulfur hexafluoride, an insulator in electrical equipment. The molecule adopts a distorted pyramidal structure, with Cs symmetry. The S-O and S-F distances are 1.42 and 1.58 Å, respectively. The O-S-F and F-S-F angles are 106.2 and 92.2°, respectively. Thionyl chloride and thionyl bromide have similar structures, although these compounds are liquid at room temperature. Mixed halides are also known, such as SOClF, thionyl chloride fluoride.

<span class="mw-page-title-main">Sulfuryl chloride</span> Chemical compound

Sulfuryl chloride is an inorganic compound with the formula SO2Cl2. At room temperature, it is a colorless liquid with a pungent odor. Sulfuryl chloride is not found in nature, as can be inferred from its rapid hydrolysis.

<span class="mw-page-title-main">Disulfur decafluoride</span> Chemical compound

Disulfur decafluoride is a chemical compound with the formula S2F10. It was discovered in 1934 by Denbigh and Whytlaw-Gray. Each sulfur atom of the S2F10 molecule is octahedral, and surrounded by five fluorine atoms and one sulfur atom. The two sulfur atoms are connected by a single bond. In the S2F10 molecule, the oxidation state of each sulfur atoms is +5, but their valency is 6. S2F10 is highly toxic, with toxicity four times that of phosgene.

<span class="mw-page-title-main">Xenon difluoride</span> Chemical compound

Xenon difluoride is a powerful fluorinating agent with the chemical formula XeF
2
, and one of the most stable xenon compounds. Like most covalent inorganic fluorides it is moisture-sensitive. It decomposes on contact with water vapor, but is otherwise stable in storage. Xenon difluoride is a dense, colourless crystalline solid.

<span class="mw-page-title-main">Sulfur tetrafluoride</span> Chemical compound

Sulfur tetrafluoride is the chemical compound with the formula SF4. It is a colorless corrosive gas that releases dangerous HF upon exposure to water or moisture. Despite these unwelcome characteristics, this compound is a useful reagent for the preparation of organofluorine compounds, some of which are important in the pharmaceutical and specialty chemical industries.

<span class="mw-page-title-main">Selenium tetrafluoride</span> Chemical compound

Selenium tetrafluoride (SeF4) is an inorganic compound. It is a colourless liquid that reacts readily with water. It can be used as a fluorinating reagent in organic syntheses (fluorination of alcohols, carboxylic acids or carbonyl compounds) and has advantages over sulfur tetrafluoride in that milder conditions can be employed and it is a liquid rather than a gas.

<span class="mw-page-title-main">Dioxygenyl</span> Chemical compound

The dioxygenyl ion, O+
2
, is a rarely-encountered oxycation in which both oxygen atoms have a formal oxidation state of +1/2. It is formally derived from oxygen by the removal of an electron:

<span class="mw-page-title-main">Fluorine perchlorate</span> Chemical compound

Fluorine perchlorate, also called perchloryl hypofluorite is the rarely encountered chemical compound of fluorine, chlorine, and oxygen with the chemical formula ClO
4
F
or FOClO
3
. It is an extremely unstable gas that explodes spontaneously and has a penetrating odor.

<span class="mw-page-title-main">Thionyl tetrafluoride</span> Chemical compound

Thionyl tetrafluoride is an inorganic compound gas with the formula SOF4. It is also known as sulfur tetrafluoride oxide. The shape of the molecule is a distorted trigonal bipyramid, with the oxygen found on the equator. The atoms on the equator have shorter bond lengths than the fluorine atoms on the axis. The sulfur oxygen bond is 1.409Å. A S−F bond on the axis has length 1.596Å and the S−F bond on the equator has length 1.539Å. The angle between the equatorial fluorine atoms is 112.8°. The angle between axial fluorine and oxygen is 97.7°. The angle between oxygen and equatorial fluorine is 123.6° and between axial and equatorial fluorine is 85.7°. The fluorine atoms only produce one NMR line, probably because they exchange positions.

<span class="mw-page-title-main">Sulfur chloride pentafluoride</span> Chemical compound

Sulfur chloride pentafluoride is an inorganic compound with the formula SF5Cl. It exists as a colorless gas at room temperature and is highly toxic, like most inorganic compounds containing the pentafluorosulfide functional group. The compound adopts an octahedral geometry with C
4v
symmetry. Sulfur chloride pentafluoride is the only commercially available reagent for adding the –SF5 group to organic compounds.

In chemistry, molecular oxohalides (oxyhalides) are a group of chemical compounds in which both oxygen and halogen atoms are attached to another chemical element A in a single molecule. They have the general formula AOmXn, where X = fluorine (F), chlorine (Cl), bromine (Br), and/or iodine (I). The element A may be a main group element, a transition element or an actinide. The term oxohalide, or oxyhalide, may also refer to minerals and other crystalline substances with the same overall chemical formula, but having an ionic structure.

<span class="mw-page-title-main">Thiophosphoryl fluoride</span> Chemical compound

Thiophosphoryl fluoride is an inorganic molecular gas with formula PSF3 containing phosphorus, sulfur and fluorine. It spontaneously ignites in air and burns with a cool flame. The discoverers were able to have flames around their hands without discomfort, and called it "probably one of the coldest flames known". The gas was discovered in 1888.

Difluoroamino sulfur pentafluoride is a gaseous chemical compound of fluorine, sulfur, and nitrogen. It is unusual in having a hexa-coordinated sulfur atom with a link to nitrogen. Other names for this substance include difluoro(pentafluorosulfur)amine, pentafluorosulfanyldifluoramine, and pentafluorosulfanyl N,N-difluoramine.

<span class="mw-page-title-main">Difluorodisulfanedifluoride</span> Chemical compound

1,1,1,2-tetrafluorodisulfane, also known as 1,2-difluorodisulfane 1,1-difluoride or just difluorodisulfanedifluoride (FSSF3) is an unstable molecular compound of fluorine and sulfur. The molecule has a pair of sulfur atoms, with one fluorine atom on one sulfur, and three fluorine atoms on the other. It has the uncommon property that all the bond lengths are different. The bond strength is not correlated with bond length but is inversely correlated with the force constant (Badger's rule). The molecule can be considered as sulfur tetrafluoride in which a sulfur atom is inserted into a S-F bond.

<span class="mw-page-title-main">Chlorine trifluoride oxide</span> Chemical compound

Chlorine oxide trifluoride or chlorine trifluoride oxide is a corrosive liquid molecular compound with formula ClOF3. It was developed secretly as a rocket fuel oxidiser.

<span class="mw-page-title-main">Seleninyl fluoride</span> Chemical compound

Seleninyl fluoride is an oxyfluoride of selenium with the chemical formula SeOF2.

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. 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. 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.