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 (IrF6 or PtF6) 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: F2 + FNO → F3NO. 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 nitrosyl hexafluoronickelate (NO)2NiF6 → ONF + ONF3 + NiF2.[4]
Propertiesedit
F3NO 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 F3NO 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 between 200 and 500 ppm.[5]
Reactionsedit
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 F2NO+ ion.[1]
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 NO2F, NOF, NO2 and NO. The oxygen remains attached to the nitrogen during decomposition.[5]
Referencesedit
^ abcdefgFox, 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.
^Powell, P. (2013). The Chemistry of the Non-Metals. Springer Science & Business Media. p. 134. ISBN978-94-011-6904-2.
^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.
^Bartlett, Neil; Passmore, J.; Wells, E. J. (1966). "Nitrogen oxide trifluoride". Chemical Communications (7): 213. doi:10.1039/C19660000213.
^ abcdefgFox, 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.
^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. Bibcode:1969JChPh..51..467K. doi:10.1063/1.1671761.
^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.
^ abFox, 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.
^Christe, Karl O.; Maya, Walter (1 June 1969). "Difluoronitronium cation, NF2O+". Inorg. Chem. 8 (6): 1253-1257. doi:10.1021/ic50076a012.
January 01, 1970
trifluoramine, oxide, nitrogen, trifluoride, oxide, f3no, inorganic, molecule, with, strong, fluorinating, powers, identifiers, number, 13847, model, jsmol, interactive, image, chemspider, 24508, pubchem, 26304, comptox, dashboard, dtxsid90160687, inchi, inchi. Trifluoramine oxide or Nitrogen trifluoride oxide F3NO is an inorganic molecule with strong fluorinating powers Trifluoramine oxide Identifiers CAS Number 13847 65 9 3D model JSmol Interactive image ChemSpider 24508 PubChem CID 26304 CompTox Dashboard EPA DTXSID90160687 InChI InChI 1S F3NO c1 4 2 3 5Key UDOZVPVDQKQJAP UHFFFAOYSA N SMILES N O F F F Properties Chemical formula F 3N O 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 Except where otherwise noted data are given for materials in their standard state at 25 C 77 F 100 kPa Infobox references Contents 1 Production 2 Properties 3 Reactions 4 ReferencesProduction editTrifluoramine 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 IrF6 or PtF6 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 F2 FNO F3NO 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 nitrosyl hexafluoronickelate NO 2NiF6 ONF ONF3 NiF2 4 Properties editF3NO 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 F3NO 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 A the N F bond length is 1 431 A the bond angles FNF is 101 and the three bond angles ONF 117 7 Trifluoramine oxide is toxic killing rats at a concentration between 200 and 500 ppm 5 Reactions editOn 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 F2NO ion 1 substrate product 8 9 comment N2F4 NF3 N2O4 NO2F Cl2 ClF SF4 SF6 H2O no reaction aqueous NaOH NO3 F slow H2SO4 HNO3 HF via F2NO SbF5 F2NO SbF6 AsF5 F2NO AsF6 PF5 no reaction BF3 F2NO BF4 F2NO B2F7 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 NO2F NOF NO2 and NO The oxygen remains attached to the nitrogen during decomposition 5 References edit a b c d e f g 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 Powell P 2013 The Chemistry of the Non Metals Springer Science amp Business Media p 134 ISBN 978 94 011 6904 2 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 Bartlett Neil Passmore J Wells E J 1966 Nitrogen oxide trifluoride Chemical Communications 7 213 doi 10 1039 C19660000213 a b c d e f g 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 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 Bibcode 1969JChPh 51 467K doi 10 1063 1 1671761 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 a b 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 Christe Karl O Maya Walter 1 June 1969 Difluoronitronium cation NF2O Inorg Chem 8 6 1253 1257 doi 10 1021 ic50076a012 Retrieved from https en wikipedia org w index php title Trifluoramine oxide amp oldid 1217345179, wikipedia, wiki, book, books, library,
