Chlorine trifluoride oxide

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Chlorine trifluoride oxide
Chlorine-trifluoride-oxide-3D-vdW.png
Chlorine-trifluoride-oxide-3D-balls.png
Names
IUPAC name
trifluoro(oxo)-λ5-chlorane
Identifiers
3D model (JSmol)
PubChem CID
  • InChI=1S/ClF3O/c2-1(3,4)5
    Key: QPKQQPNQDSQNHS-UHFFFAOYSA-N
  • O=Cl(F)(F)F
Properties
ClF3O
Molar mass 108.44 g·mol−1
Density 1.865
Melting point −42 °C (−44 °F; 231 K)
Boiling point 29 °C (84 °F; 302 K)
Structure
monoclinic
C2/m
a = 9.826, b = 12.295, c = 4.901
α = 90°, β = 90.338°, γ = 90° [2]
592.1
8
Hazards
GHS labelling:
GHS-pictogram-rondflam.svg GHS-pictogram-acid.svg GHS-pictogram-skull.svg GHS-pictogram-pollu.svg
Danger
Related compounds
Related compounds
BrOF3; IOF3
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

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.

Contents

Production

Chlorine oxide trifluoride was originally made at Rocketdyne [3] by treating dichlorine monoxide with fluorine. Other substances that could react with fluorine to make it includes sodium chlorite (NaClO2), and chlorine nitrate (ClONO2). The first published production method was a reaction of dichlorine monoxide with oxygen difluoride (OF2). Yet other production methods are reactions between ClO2F or ClO3F and chlorine fluorides. [4] A safer approach is the use chlorine nitrate with fluorine.

Reactions

As a Lewis base it can lose a fluoride ion to Lewis acids, yielding the difluorooxychloronium(V) cation (ClOF2+). [5] Compounds with this include: ClOF2BF4, ClOF2PF6, ClOF2AsF6, ClOF2SbF6, ClOF2BiF6, ClOF2VF6, ClOF2NbF6, ClOF2TaF6, ClOF2UF6, ClOF2, (ClOF2)2SiF6, ClOF2MoOF5, ClOF2Mo2O4F9, [4] ClOF2PtF6. [6]

Functioning as a Lewis acid, it can gain a fluoride ion from a strong base to yield a tetrafluorooxychlorate(V) anion: ClOF4 ion. [7] These include KClOF4, RbClOF4, and CsClOF4. [8] This allows purification of ClOF3, as at room temperature a solid complex is formed, but this decomposes between 50 and 70 °C. Other likely impurities either will not react with alkali fluoride, or if they do will not easily decompose. [3]

Chlorine trifluoride oxide fluoridates various materials such as chlorine monoxide, chlorine, glass or quartz. [3] ClOF3 + Cl2O → 2ClF + ClO2F; [6] 2ClOF3 + 2Cl2 → 6ClF + O2 at 200 °C [6]

Chlorine trifluoride oxide adds to chlorine fluorosulfate, ClOF3 + 2ClOSO2F → S2O5F2 + FClO2 + 2ClF. The reaction also produces SO2F2. [3]

Chlorine trifluoride oxide can fluoridate and add oxygen in the same reaction, reacting with molybdenum pentafluoride, silicon tetrafluoride, tetrafluorohydrazine (over 100 °C), HNF2, and F2NCOF. From HNF2 the main result was NF3O. From MoF5, the results were MoF6 and MoOF4. [3]

It reacts explosively with hydrocarbons. [3] With small amounts of water, ClO2F is formed along with HF. [3]

Over 280 °C ClOF3 decomposes to oxygen and chlorine trifluoride. [3]

Properties

The boiling point of chlorine trifluoride oxide is 29 °C. [9]

The shape of the molecule is a trigonal bipyramid, with two fluorine atoms at the top and bottom (apex) (Fa) and an electron pair, oxygen and fluorine (Fe) on the equator. [7] The Cl=O bond length is 1.405 Å, Cl-Fe 1.603 Å, other Cl-Fa 1.713 Å, ∠FeClO=109° ∠FaClO=95°, ∠FaClFe=88°. The molecule is polarised, Cl has a +1.76 charge, O has −0.53, equatorial F has −0.31 and apex F has −0.46. The total dipole moment is 1.74 D. [10]

Related Research Articles

In chemistry, an interhalogen compound is a molecule which contains two or more different halogen atoms and no atoms of elements from any other group.

<span class="mw-page-title-main">Oxygen fluoride</span> Any binary compound of oxygen and fluorine

Oxygen fluorides are compounds of elements oxygen and fluorine with the general formula OnF2, where n = 1 to 6. Many different oxygen fluorides are known:

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

Dichlorine monoxide is an inorganic compound with the molecular formula Cl2O. It was first synthesised in 1834 by Antoine Jérôme Balard, who along with Gay-Lussac also determined its composition. In older literature it is often referred to as chlorine monoxide, which can be a source of confusion as that name now refers to the ClO radical.

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

Chlorine pentafluoride is an interhalogen compound with formula ClF5. This colourless gas is a strong oxidant that was once a candidate oxidizer for rockets. The molecule adopts a square pyramidal structure with C4v symmetry, as confirmed by its high-resolution 19F NMR spectrum. It was first synthesized in 1963.

<span class="mw-page-title-main">Cobalt(III) fluoride</span> Chemical compound

Cobalt(III) fluoride is the inorganic compound with the formula CoF3. Hydrates are also known. The anhydrous compound is a hygroscopic brown solid. It is used to synthesize organofluorine compounds.

<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.

Bromine compounds are compounds containing the element bromine (Br). These compounds usually form the -1, +1, +3 and +5 oxidation states. Bromine is intermediate in reactivity between chlorine and iodine, and is one of the most reactive elements. Bond energies to bromine tend to be lower than those to chlorine but higher than those to iodine, and bromine is a weaker oxidising agent than chlorine but a stronger one than iodine. This can be seen from the standard electrode potentials of the X2/X couples (F, +2.866 V; Cl, +1.395 V; Br, +1.087 V; I, +0.615 V; At, approximately +0.3 V). Bromination often leads to higher oxidation states than iodination but lower or equal oxidation states to chlorination. Bromine tends to react with compounds including M–M, M–H, or M–C bonds to form M–Br bonds.

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

Chloryl fluoride is the chemical compound with the formula ClO2F. It is commonly encountered as side-product in reactions of chlorine fluorides with oxygen sources. It is the acyl fluoride of chloric acid.

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

Chlorine nitrate, with chemical formula ClNO3 is an important atmospheric gas present in the stratosphere. It is an important sink of chlorine that contributes to the depletion of ozone.

<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">Tetrafluoroammonium</span>

The tetrafluoroammonium cation is a positively charged polyatomic ion with chemical formula NF+
4
. It is equivalent to the ammonium ion where the hydrogen atoms surrounding the central nitrogen atom have been replaced by fluorine. Tetrafluoroammonium ion is isoelectronic with tetrafluoromethane CF
4
, trifluoramine oxide ONF
3
and the tetrafluoroborate BF
4
anion.

<span class="mw-page-title-main">Chloryl</span> Ion

In chemistry, chloryl refers to a triatomic cation with chemical formula ClO+
2
. This species has the same general structure as chlorite (ClO
2
) but it is electronically different, with chlorine having a +5 oxidation state (rather than the +3 of chlorite). This makes it a rare example of a positively charged oxychloride. Chloryl compounds, such as FClO
2
and [ClO2][RuF6], are all highly reactive and react violently with water and most organic compounds.

Boron monofluoride or fluoroborylene is a chemical compound with formula BF, one atom of boron and one of fluorine. It was discovered as an unstable gas and only in 2009 found to be a stable ligand combining with transition metals, in the same way as carbon monoxide. It is a subhalide, containing fewer than the normal number of fluorine atoms, compared with boron trifluoride. It can also be called a borylene, as it contains boron with two unshared electrons. BF is isoelectronic with carbon monoxide and dinitrogen; each molecule has 14 electrons.

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

Chromyl fluoride is an inorganic compound with the formula CrO2F2. It is a violet-red colored crystalline solid that melts to an orange-red liquid.

<span class="mw-page-title-main">Potassium hexafluoronickelate(IV)</span> Chemical compound

Potassium hexafluoronickelate(IV) is an inorganic compound with the chemical formula K
2
NiF
6
. It can be produced through the reaction of potassium fluoride, nickel dichloride, and fluorine.

<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.

Nitrogen pentafluoride (NF5) is a theoretical compound of nitrogen and fluorine that is hypothesized to exist based on the existence of the pentafluorides of the atoms below nitrogen in the periodic table, such as phosphorus pentafluoride. Theoretical models of the nitrogen pentafluoride molecule are either a trigonal bipyramidal covalently bound molecule with symmetry group D3h, or NF+
4
F, which would be an ionic solid.

Fluorine forms a great variety of chemical compounds, within which it always adopts an oxidation state of −1. With other atoms, fluorine forms either polar covalent bonds or ionic bonds. Most frequently, covalent bonds involving fluorine atoms are single bonds, although at least two examples of a higher order bond exist. Fluoride may act as a bridging ligand between two metals in some complex molecules. Molecules containing fluorine may also exhibit hydrogen bonding. Fluorine's chemistry includes inorganic compounds formed with hydrogen, metals, nonmetals, and even noble gases; as well as a diverse set of organic compounds. For many elements the highest known oxidation state can be achieved in a fluoride. For some elements this is achieved exclusively in a fluoride, for others exclusively in an oxide; and for still others the highest oxidation states of oxides and fluorides are always equal.

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

Trifluoramine oxide or Nitrogen trifluoride oxide (F3NO) is an inorganic molecule with strong fluorinating powers.

Iodosyl pentafluoride is an inorganic compound of iodine, fluorine, and oxygen with the chemical formula IOF5.

References

  1. Urben, Peter (2017). Bretherick's Handbook of Reactive Chemical Hazards. Elsevier. p. 784. ISBN   9780081010594.
  2. Ellern, Arkady; Boatz, Jerry A.; Christe, Karl O.; Drews, Thomas; Seppelt, Konrad (September 2002). "The Crystal Structures of ClF3O, BrF3O, and [NO]+[BrF4O]". Zeitschrift für anorganische und allgemeine Chemie. 628 (9–10): 1991–1999. doi:10.1002/1521-3749(200209)628:9/10<1991::AID-ZAAC1991>3.0.CO;2-1.
  3. 1 2 3 4 5 6 7 8 Advances in Inorganic Chemistry and Radiochemistry. Academic Press. 1976. pp. 331–333. ISBN   9780080578675.
  4. 1 2 Holloway, John H.; Laycock, David (1983). Advances in Inorganic Chemistry. Academic Press. pp. 178–179. ISBN   9780080578767.
  5. Christe, Karl O.; Curtis, E. C.; Schack, Carl J. (September 1972). "Chlorine trifluoride oxide. VII. Difluorooxychloronium(V) cation, ClF2O+. Vibrational spectrum and force constants". Inorganic Chemistry. 11 (9): 2212–2215. doi:10.1021/ic50115a046.
  6. 1 2 3 Schack, Carl J.; Lindahl, C. B.; Pilipovich, Donald.; Christe, Karl O. (September 1972). "Chlorine trifluoride oxide. IV. Reaction chemistry". Inorganic Chemistry. 11 (9): 2201–2205. doi:10.1021/ic50115a043.
  7. 1 2 Christe, K.O.; Schack, C.J. (1976). Chlorine Oxyfluorides. Advances in Inorganic Chemistry and Radiochemistry. Vol. 18. pp. 319–398. doi:10.1016/S0065-2792(08)60033-3. ISBN   9780120236183.
  8. Christe, Karl O.; Schack, Carl J.; Pilipovich, Donald.; Christe, Karl O. (September 1972). "Chlorine trifluoride oxide. V. Complex formation with Lewis acids and bases". Inorganic Chemistry. 11 (9): 2205–2208. doi:10.1021/ic50115a044.
  9. Pilipovich, Donald.; Lindahl, C. B.; Schack, Carl J.; Wilson, R. D.; Christe, Karl O. (September 1972). "Chlorine trifluoride oxide. I. Preparation and properties". Inorganic Chemistry. 11 (9): 2189–2192. doi:10.1021/ic50115a040.
  10. Oberhammer, Heinz.; Christe, Karl O. (January 1982). "Gas-phase structure of chlorine trifluoride oxide, ClF3O". Inorganic Chemistry. 21 (1): 273–275. doi:10.1021/ic00131a050.