Dinitrogen difluoride

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Dinitrogen difluoride [1]
(Z)-Dinitrogen-difluoride.png
cis-dinitrogen difluoride
(E)-Dinitrogen-difluoride.png
trans-dinitrogen difluoride
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(E)-Dinitrogen-difluoride-3D-balls.png
Names
IUPAC name
cis- or trans-dinitrogen difluoride
Other names
cis- or trans-difluorodiazene
Identifiers
3D model (JSmol)
ChemSpider
PubChem CID
  • (cis):InChI=1S/F2N2/c1-3-4-2/b4-3-
    Key: DUQAODNTUBJRGF-ONEGZZNKBY
  • (trans):InChI=1/F2N2/c1-3-4-2/b4-3+
    Key: DUQAODNTUBJRGF-ONEGZZNKBY
  • InChI=1S/F2N2/c1-3-4-2/b4-3+ Yes check.svgY
    Key: DUQAODNTUBJRGF-ARJAWSKDSA-N Yes check.svgY
  • (cis):F\N=N\F
  • (trans):F\N=N/F
Properties
FN=NF
Molar mass 66.011 g·mol−1
AppearanceColorless gas
Density 2.698 g/L
Melting point cis: less than−195 °C (−319.0 °F; 78.1 K)
trans: −172 °C (−278 °F)
Boiling point cis:−105.75 °C (−158.35 °F; 167.40 K)
trans: −111.45 °C (−168.61 °F)
cis: 0.16 D
trans: 0 D
Thermochemistry
cis: 69.5 kJ/mol
trans: 82.0 kJ/mol
Related compounds
Other anions
Azide
Other cations
Related compounds
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Dinitrogen difluoride is a chemical compound with the formula N2F2. It is a gas at room temperature, and was first identified in 1952 as the thermal decomposition product of the fluorine azide (FN3). It has the structure F−N=N−F and exists in both cis and trans isomers, as typical for diimides.

Contents

Isomers

The cis isomer has C2v symmetry and the trans isomer has C2h symmetry. These isomers can interconvert, but the process is slow enough at low temperature that the two can separated by low-temperature fractionation.[ clarification needed ] The trans isomer is less thermodynamically stable [2] but can be stored in glass vessels. The cis isomer attacks glass over a time scale of about 2 weeks to form silicon tetrafluoride and nitrous oxide: [3] [ page needed ]

2 N2F2 + SiO2 → SiF4 + 2 N2O

Preparation

Most preparations of dinitrogen difluoride give mixtures of the two isomers, but they can be prepared independently.

An aqueous method involves N,N-difluorourea with concentrated potassium hydroxide. This gives a 40% yield with three times more of the trans isomer. [4]

Difluoramine forms a solid unstable compound with potassium fluoride (or rubidium fluoride or caesium fluoride) which decomposes to dinitrogen difluoride. [4]

It can also be prepared by photolysis of tetrafluorohydrazine and bromine: [5]

N2F4hvBr2N2F2 + byproducts

Reactions

The cis form of difluorodiazene will react with strong fluoride ion acceptors such as antimony pentafluoride to form the linear [6] [N≡N−F]+ cation (fluorodiazonium cation [6] ) which forms a salt with the formula [N≡N−F]+[SbF6] (fluorodiazonium hexafluoroantimonate(V)).

F−N=N−F + SbF5[N≡N−F]+[SbF6]

Analogous reaction of cis-difluorodiazene with arsenic pentafluoride gives white solid salt with the formula [N≡N−F]+[AsF6] [6] (fluorodiazonium hexafluoroarsenate(V)).

F−N=N−F + AsF5[N≡N−F]+[AsF6]

In the solid phase, the observed N≡N and N−F bond distances in the [N≡N−F]+ cation are 1.089(9) and 1.257(8) Å respectively, among the shortest experimentally observed N-N and N-F bonds.

References

  1. Lide, David R. (1998). Handbook of Chemistry and Physics (87th ed.). Boca Raton, FL: CRC Press. pp. 4–73, 5–15, 9–46. ISBN   0-8493-0594-2.
  2. Christe, Karl O.; Dixon, David A.; Grant, Daniel J.; Haiges, Ralf; Tham, Fook S.; Vij, Ashwani; Vij, Vandana; Wang, Tsang-Hsiu; Wilson, William W. (2010-08-02). "Dinitrogen Difluoride Chemistry. Improved Syntheses of cis - and trans -N 2 F 2 , Synthesis and Characterization of N 2 F + Sn 2 F 9 − , Ordered Crystal Structure of N 2 F + Sb 2 F 11 − , High-Level Electronic Structure Calculations of cis -N 2 F 2 , trans -N 2 F 2 , F 2 N═N, and N 2 F + , and Mechanism of the trans−cis Isomerization of N 2 F 2" . Inorganic Chemistry. 49 (15): 6823–6833. doi:10.1021/ic100471s. ISSN   0020-1669. PMID   20465274.
  3. Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN   978-0-08-037941-8.
  4. 1 2 Sykes, A. G. (1989-07-17). Advances in Inorganic Chemistry. Academic Press. p. 171. ISBN   9780080578828 . Retrieved 21 June 2014.
  5. Leon M. Zaborowski; et al. (1973), Aaron Wold and John K. Ruff (ed.), Chlorodifluoroamine and Difluorodiazene - B. Difluorodiazene (Dinitrogen difluoride), Inorganic Syntheses (in German), vol. 14, McGraw-Hill Book Company, Inc., pp. 34–39
  6. 1 2 3 Cacace, Fulvio; Grandinetti, Felice; Pepi, Federico (1995). "Gaseous Fluorodiazonium Ions. Experimental and Theoretical Study on Formation and Structure of FN2+" . Inorganic Chemistry. 34 (6): 1325–1332. doi:10.1021/ic00110a007.