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| Names | |
|---|---|
| IUPAC name trifluoro(oxo)-λ5-chlorane | |
| Other names Chlorosyl trifluoride | |
| Identifiers | |
3D model (JSmol) | |
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| |
| Properties | |
| ClOF3 | |
| Molar mass | 108.44 g·mol−1 |
| Appearance | Colorless liquid |
| Density | 1.865 g/cm3 |
| 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] | |
Lattice volume (V) | 592.1 |
Formula units (Z) | 8 |
| Hazards | |
| GHS labelling: | |
    | |
| Danger | |
| Related compounds | |
Related compounds | |
Except where otherwise noted, data are given for materials in theirstandard state (at 25 °C [77 °F], 100 kPa). | |
Chlorine oxide trifluoride orchlorine trifluoride oxide is a corrosive colorless liquid molecular compound with formulaClOF3. It was developed secretly as a rocket fuel oxidiser.
Chlorine oxide trifluoride was originally made atRocketdyne[3] by treatingdichlorine monoxide withfluorine. Other substances that could react with fluorine to make it includessodium chloriteNaClO2, andchlorine nitrateCl−O−NO2. The first published production method was a reaction of dichlorine monoxide withoxygen difluorideOF2. Yet other production methods are reactions betweenClO2F orClO3F and chlorine fluorides.[4] A safer approach is the usechlorine nitrate with fluorine.
As aLewis base it can lose a fluoride ion to Lewis acids, yielding the difluorooxochloronium(V)cation[ClOF2]+.[5] Compounds with this include:[ClOF2]+[BF4]−,[ClOF2]+[PF6]−,[ClOF2]+[AsF6]−,[ClOF2]+[SbF6]−,[ClOF2]+[BiF6]−,[ClOF2]+[VF6]−,[ClOF2]+[NbF6]−,[ClOF2]+[TaF6]−,[ClOF2]+[UF6]−,([ClOF2]+)2[SiF6]2−,[ClOF2]+[MoOF5]−,[ClOF2]+[Mo2O4F9]−,[4][ClOF2]+[PtF6].[6]
Functioning as a Lewis acid, it can gain a fluoride ion from a strong base to yield a tetrafluorooxochlorate(V)anionClOF−4.[7] These includeK+[ClOF4]− (potassium tetrafluorooxochlorate(V)),Rb+[ClOF4]− (rubidium tetrafluorooxochlorate(V)), andCs+[ClOF4]− (caesium tetrafluorooxochlorate(V)). These three salts are white crystalline solids.[4][8] This allows purification ofClOF3, 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]
Chlorine trifluoride oxide adds tochlorine fluorosulfate:
The reaction also producesSO2F2.[3]
Chlorine trifluoride oxide can fluoridate and add oxygen in the same reaction, reacting withmolybdenum pentafluoride,silicon tetrafluoride,tetrafluorohydrazine (over 100 °C),HNF2, andF2NCOF. FromHNF2 the main result wasNF3O. FromMoF5, the results wereMoF6 andMoOF4.[3]
It reacts explosively with hydrocarbons.[3] With small amounts of water,ClO2F is formed along withHF.[3]
Over 280 °CClOF3 decomposes to oxygen andchlorine trifluoride.[3]
The boiling point of chlorine trifluoride oxide is 29 °C.[9]
The shape of the molecule is atrigonal 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]
