Chemistry:Trifluoramine oxide

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Trifluoramine oxide
Identifiers
3D model (JSmol)
ChemSpider
Properties
F3NO
Molar mass 87.001 g·mol−1
Appearance Colourless gas
Melting point −161 °C (−258 °F; 112 K)
Boiling point −87.5 °C (−125.5 °F; 185.7 K)
Related compounds
Related compounds
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references
Tracking categories (test):

Trifluoramine oxide or nitrogen trifluoride oxide is an inorganic molecule with the chemical formula F
3NO. It has 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 (IrF
6 or PtF
6) with nitric oxide.[1] 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.[1]

An alternate way to produce it is by burning nitric acid in fluorine, followed by rapid cooling.[2] Yet another way is the photochemical reaction of fluorine and nitrosyl fluoride:

F
2 + FNO → F
3NO

This reaction can also happen with heat, but hot fluorine is hard to contain without a reaction with the container.[3] yet another production route is to thermally decompose nitrosonium hexafluoronickelate(IV):

[NO]
2[NiF
6] → ONF + ONF
3 + NiF
2[4]

Properties

F
3NO is a colourless gas at standard conditions. It has a critical temperature of 29.5 °C where the density is 0.593 g/cm3. Critical pressure is about 64 atmospheres.[5]

Trifluoramine oxide has a Trouton's constant of 20.7.[5] Heat of vapourisation at the boiling point is 3.85 kcal/mol.[5]

The F
3NO molecule has C3V 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.[1] The nuclear magnetic resonance (NMR) spectrum of 19F has a triplet line around −363 ppm. JNF is 136 Hz.[1] The infra red spectrum N-O stretch at 1687 cm−1, N-F stretch at 743 cm−1, unsymmetrical N-F stretch 887 cm−1 ∠ONF bend 528 cm−1, wither other bands at 558, 528, 801, 929, 1055, 1410, 1622, 1772, 2435, and 3345 cm−1.[1] The dipole moment is 0.0390 D.[6]

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.[5] 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.[7]

Trifluoramine oxide is toxic, killing rats at a concentration over 200 ppm.[5]

Reactions

On fluorinating other compounds nitrosyl fluoride (NOF) is formed.[8] Trifluoramine oxide does not react with water, glass or nickel, making it easier to handle.[1] The "adducts" formed with the pentafluorides, are actually hexafluoride salts containing the [F
2NO]+
 ion (difluorooxoammonium cation).[1]

substrate product[8][9] comment
N
2F
4 		NF
3
N
2O
4 		NO
2F
Cl
2 		ClF
SF
4 		SF
6
H
2O 		no reaction
aqueous NaOH NO−
3, F−
 		slow
H
2SO
4 		HNO
3, HF 		via [F
2NO]+
SbF
5 		[F
2NO]+
[SbF
6]−
AsF
5 		[F
2NO]+
[AsF
6]−
PF
5 		no reaction
BF
3 		[F
2NO]+
[BF
4]−
, [F
2NO]+
[B
2F
7]−

Trifluoramine oxide reacts slowly with mercury, producing mercury fluorides, and nitrogen oxides.[5] Trifluoramine oxide is fairly stable when heated to 300 °C but slowly breaks up to fluorine and NO
2F, NOF, NO
2 and NO. The oxygen remains attached to the nitrogen during decomposition.[5]

References

  1. ↑ 1.0 1.1 1.2 1.3 1.4 1.5 1.6 Fox, W. B.; MacKenzie, J. S.; Vanderkooi, N.; Sukornick, B.; Wamser, C. A.; Holmes, J. R.; Eibeck, R. E.; Stewart, B. B. (June 1966). "Trifluoramine Oxide". Journal of the American Chemical Society 88 (11): 2604–2605. doi:10.1021/ja00963a051. Bibcode: 1966JAChS..88.2604F. 
  2. ↑ Powell, P. (2013) (in en). The Chemistry of the Non-Metals. Springer Science & Business Media. p. 134. ISBN 978-94-011-6904-2. https://books.google.com/books?id=4a-3BgAAQBAJ&pg=PA134. 
  3. ↑ Fox, W.B.; MacKenzie, J.S.; Vitek, R. (February 1970). "The chemistry of trifluoramine oxide. V. Synthesis of F3 no by photochemical fluorination of nitrosyl fluoride". Inorganic and Nuclear Chemistry Letters 6 (2): 177–179. doi:10.1016/0020-1650(70)80336-1. 
  4. ↑ Bartlett, Neil; Passmore, J.; Wells, E. J. (1966). "Nitrogen oxide trifluoride". Chemical Communications (7): 213. doi:10.1039/C19660000213. 
  5. ↑ 5.0 5.1 5.2 5.3 5.4 5.5 5.6 Fox, W. B.; MacKenzie, J. S.; McCarthy, E. R.; Holmes, J. R.; Stahl, R. F.; Juurik, R. (October 1968). "Chemistry of trifluoramine oxide. I. Synthesis and characterization of trifluoramine". Inorganic Chemistry 7 (10): 2064–2067. doi:10.1021/ic50068a022. 
  6. ↑ Kirchhoff, William H.; Lide, David R. (July 1969). "Microwave Spectrum, Dipole Moment, and Quadrupole Coupling Constant of Trifluoramine Oxide". The Journal of Chemical Physics 51 (1): 467–468. doi:10.1063/1.1671761. Bibcode: 1969JChPh..51..467K. 
  7. ↑ Plato, Vernon; Hartford, William D.; Hedberg, Kenneth (November 1970). "Electron-Diffraction Investigation of the Molecular Structure of Trifluoramine Oxide, F3NO". The Journal of Chemical Physics 53 (9): 3488–3494. doi:10.1063/1.1674522. 
  8. ↑ 8.0 8.1 Fox, William B.; Wamser, C. A.; Eibeck, R.; Huggins, D. K.; MacKenzie, James S.; Juurik, R. (June 1969). "Chemistry of trifluoroamine oxide. II. Reactions with inorganic substrates". Inorganic Chemistry 8 (6): 1247–1249. doi:10.1021/ic50076a010. 
  9. ↑ Christe, Karl O.; Maya, Walter (1 June 1969). "Difluoronitronium cation, NF2O+". Inorg. Chem. 8 (6): 1253–1257. doi:10.1021/ic50076a012. 



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