View source for Trifluoramine oxide

{{Chembox
| ImageFileL1    = Trifluoramine oxide.svg
| ImageSizeL1    = 80px
| ImageFileR1    = Trifluoroamine-oxide-3D-balls.png
| ImageSizeR1    = 120px
| Section1       = {{Chembox Identifiers
| CASNo = 13847-65-9
| ChemSpiderID = 24508
| PubChem = 26304
| StdInChI=1S/F3NO/c1-4(2,3)5
| StdInChIKey = UDOZVPVDQKQJAP-UHFFFAOYSA-N
| SMILES = [N+]([O-])(F)(F)F
}}
| Section2       = {{Chembox Properties
|N=1|O=1|F=3
| Appearance = Colourless gas
| MeltingPtC = −161
| BoilingPtC = −87.5
}}
}}
'''Trifluoramine oxide''' or '''Nitrogen trifluoride oxide''' ('''F<sub>3</sub>NO''') is an inorganic molecule with strong fluorinating powers.

==Production==
Trifluoramine oxide was first discovered in 1966 independently by two different groups. One way to produce it was by an electric discharge in a mixture of oxygen on [[nitrogen trifluoride]]. Another even less yielding method is by reacting noble metal fluorides ([[iridium hexafluoride|IrF<sub>6</sub>]] or [[platinum hexafluoride|PtF<sub>6</sub>]]) with [[nitric oxide]].<ref name="fox0">{{cite journal |last1=Fox |first1=W. B. |last2=MacKenzie |first2=J. S. |last3=Vanderkooi |first3=N. |last4=Sukornick |first4=B. |last5=Wamser |first5=C. A. |last6=Holmes |first6=J. R. |last7=Eibeck |first7=R. E. |last8=Stewart |first8=B. B. |title=Trifluoramine Oxide |journal=Journal of the American Chemical Society |date=June 1966 |volume=88 |issue=11 |pages=2604–2605 |doi=10.1021/ja00963a051}}</ref> It is separated by distillation, and can be purified by treating it with [[potassium hydroxide]] solution which reacts with the other fluorine containing molecules produced.<ref name="fox0"/>

An alternate way to produce it is by burning nitric acid in fluorine, followed by rapid cooling.<ref>{{cite book |last1=Powell |first1=P. |title=The Chemistry of the Non-Metals |date=2013 |publisher=Springer Science & Business Media |isbn=978-94-011-6904-2 |page=134 |url=https://books.google.com/books?id=4a-3BgAAQBAJ&pg=PA134 |language=en}}</ref> Yet another way is the photochemical reaction of fluorine and [[nitrosyl fluoride]]: F<sub>2</sub> + FNO → F<sub>3</sub>NO.  This reaction can also happen with heat, but hot fluorine is hard to contain without a reaction with the container.<ref>{{cite journal |last1=Fox |first1=W.B. |last2=MacKenzie |first2=J.S. |last3=Vitek |first3=R. |title=The chemistry of trifluoramine oxide. V. Synthesis of F3 no by photochemical fluorination of nitrosyl fluoride |journal=Inorganic and Nuclear Chemistry Letters |date=February 1970 |volume=6 |issue=2 |pages=177–179 |doi=10.1016/0020-1650(70)80336-1}}</ref> yet another production route is to thermally decompose nitrosyl hexafluoronickelate (NO)<sub>2</sub>NiF<sub>6</sub> → ONF + ONF<sub>3</sub> + NiF<sub>2</sub>.<ref>{{cite journal |last1=Bartlett |first1=Neil |last2=Passmore |first2=J. |last3=Wells |first3=E. J. |title=Nitrogen oxide trifluoride |journal=Chemical Communications |date=1966 |issue=7 |pages=213 |doi=10.1039/C19660000213}}</ref>

==Properties==
F<sub>3</sub>NO is a colourless gas at standard conditions. It has a critical temperature of 29.5&nbsp;°C where the density is 0.593 g/cm<sup>3</sup>. Critical pressure is about 64 atmospheres.<ref name=fox68/>

Trifluoramine oxide has a [[Trouton's constant]] of 20.7.<ref name=fox68/> Heat of vapourisation at the boiling point is 3.85 kcal/mol.<ref name=fox68/>

The F<sub>3</sub>NO molecule has C<sub>3V</sub> symmetry, with all the N-F bonds being equivalent.  The shape is almost a tetrahedron as N-O bond is similar to the N-F bonds in nature.<ref name="fox0"/>
The [[nuclear magnetic resonance]] (NMR) spectrum of <sup>19</sup>F has a triplet line around −363 ppm. J<sub>NF</sub> is 136&nbsp;Hz.<ref name="fox0"/>
The infra red spectrum N-O stretch at 1687&nbsp;cm<sup>−1</sup>, N-F stretch at 743&nbsp;cm<sup>−1</sup>, unsymmetrical N-F stretch 887&nbsp;cm<sup>−1</sup> ∠ONF bend 528&nbsp;cm<sup>−1</sup>, wither other bands at 558, 528, 801, 929, 1055, 1410, 1622, 1772, 2435, and 3345&nbsp;cm<sup>−1</sup>.<ref name="fox0"/> The dipole moment is 0.0390 D.<ref>{{cite journal |last1=Kirchhoff |first1=William H. |last2=Lide |first2=David R. |title=Microwave Spectrum, Dipole Moment, and Quadrupole Coupling Constant of Trifluoramine Oxide |journal=The Journal of Chemical Physics |date=July 1969 |volume=51 |issue=1 |pages=467–468 |doi=10.1063/1.1671761|bibcode=1969JChPh..51..467K }}</ref>

The N-O bond has 75% double bond character.  This differs from the [[amine oxides]] where the amine is much more basic and with a positive charge.<ref name=fox68>{{cite journal |last1=Fox |first1=W. B. |last2=MacKenzie |first2=J. S. |last3=McCarthy |first3=E. R. |last4=Holmes |first4=J. R. |last5=Stahl |first5=R. F. |last6=Juurik |first6=R. |title=Chemistry of trifluoramine oxide. I. Synthesis and characterization of trifluoramine |journal=Inorganic Chemistry |date=October 1968 |volume=7 |issue=10 |pages=2064–2067 |doi=10.1021/ic50068a022}}</ref> The N-O bond-length is 1.158 Å; the N–F bond-length is  1.431 Å ; the bond angles ∠FNF  is  101°; and the three bond angles ∠ONF = 117.<ref>{{cite journal |last1=Plato |first1=Vernon |last2=Hartford |first2=William D. |last3=Hedberg |first3=Kenneth |title=Electron-Diffraction Investigation of the Molecular Structure of Trifluoramine Oxide, F3NO |journal=The Journal of Chemical Physics |date=November 1970 |volume=53 |issue=9 |pages=3488–3494 |doi=10.1063/1.1674522}}</ref>

Trifluoramine oxide is toxic, killing rats at a concentration between 200 and 500 ppm.<ref name=fox68/>

==Reactions==
On fluorinating other compounds [[nitrosyl fluoride]] (NOF) is formed.<ref name=fox1>{{cite journal|last1=Fox|first1=William B.|last2=Wamser|first2=C. A.|last3=Eibeck|first3=R.|last4=Huggins|first4=D. K.|last5=MacKenzie|first5=James S.|last6=Juurik|first6=R.|title=Chemistry of trifluoroamine oxide. II. Reactions with inorganic substrates|journal=Inorganic Chemistry|date=June 1969|volume=8|issue=6|pages=1247–1249|doi=10.1021/ic50076a010}}</ref>
Trifluoramine oxide does not react with water, glass or [[nickel]], making it easier to handle.<ref name="fox0"/>
The "adducts" formed with the pentafluorides, are actually hexafluoride salts containing the F<sub>2</sub>NO<sup>+</sup> ion.<ref name="fox0"/>
{|class="wikitable"
!substrate
!product<ref name=fox1/><ref>{{cite journal|last1=Christe|first1=Karl O.|last2=Maya|first2=Walter|title=Difluoronitronium cation, NF2O+|journal=Inorg. Chem.|volume=8|issue=6|date=1 June 1969|page=1253-1257|doi=10.1021/ic50076a012}}</ref>
!comment
|-
|[[dinitrogen tetrafluoride|N<sub>2</sub>F<sub>4</sub>]]
|[[nitrogen trifluoride|NF<sub>3</sub>]]
|-
|[[dinitrogen tetroxide|N<sub>2</sub>O<sub>4</sub>]]
|[[Nitryl fluoride|NO<sub>2</sub>F]]
|-
|Cl<sub>2</sub>
|[[chlorine monofluoride|ClF]]
|-
|[[sulfur tetrafluoride|SF<sub>4</sub>]]
|[[sulfur hexafluoride|SF<sub>6</sub>]]
|-
|H<sub>2</sub>O
|
|no reaction
|-
|aqueous NaOH
|[[nitrate|NO<sub>3</sub><sup>−</sup>]], [[fluoride|F<sup>−</sup>]]
|slow
|-
|[[sulfuric acid|H<sub>2</sub>SO<sub>4</sub>]]
|[[nitric acid|HNO<sub>3</sub>]],HF
|via F<sub>2</sub>NO<sup>+</sup>
|-
|[[antimony pentafluoride|SbF<sub>5</sub>]]
|F<sub>2</sub>NO<sup>+</sup>SbF<sub>6</sub><sup>−</sup>
|-
|[[arsenic pentafluoride|AsF<sub>5</sub>]]
|F<sub>2</sub>NO<sup>+</sup>AsF<sub>6</sub><sup>−</sup>
|-
|[[phosphorus pentafluoride|PF<sub>5</sub>]]
|
|no reaction
|-
|[[boron trifluoride|BF<sub>3</sub>]]
|F<sub>2</sub>NO<sup>+</sup>BF<sub>4</sub><sup>−</sup>,F<sub>2</sub>NO<sup>+</sup>B<sub>2</sub>F<sub>7</sub><sup>−</sup>
|-
|}

Trifluoramine oxide reacts slowly with mercury, producing [[mercury fluoride]]s, and nitrogen oxides.<ref name=fox68/> Trifluoramine oxide is fairly stable when heated to 300&nbsp;°C but slowly breaks up to fluorine and NO<sub>2</sub>F, NOF, NO<sub>2</sub> and NO. The oxygen remains attached to the nitrogen during decomposition.<ref name=fox68/>

==References==
{{Reflist}}

[[Category:Nitrogen oxohalides]]
[[Category:Nitrogen(V) compounds]]
[[Category:Oxyfluorides]]