Dinitrogen difluoride

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Dinitrogen difluoride[1]
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Molar mass Template:Chem molar mass
Appearance Colorless gas
Density 2.698 g/L
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Template:Longitem cis: 0.16 D
trans: 0 D
Template:Longitem cis: 69.5 kJ/mol
trans: 82.0 kJ/mol
Template:Longitem Azide
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Dinitrogen difluoride is a chemical compound with the formula Template:Chem2. It is a gas at room temperature, and was first identified in 1952 as the thermal decomposition product of the fluorine azide (Template:Chem2). It has the structure Template:Chem2 and exists in both cis and trans isomers, as typical for diimides.

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.Script error: No such module "Unsubst". 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]Script error: No such module "Unsubst".

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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]

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Reactions

The cis form of difluorodiazene will react with strong fluoride ion acceptors such as antimony pentafluoride to form the linear[6] Template:Chem2 cation (fluorodiazonium cation[6]) which forms a salt with the formula Template:Chem2 (fluorodiazonium hexafluoroantimonate(V)).

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Analogous reaction of cis-difluorodiazene with arsenic pentafluoride gives white solid salt with the formula Template:Chem2[6] (fluorodiazonium hexafluoroarsenate(V)).

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In the solid phase, the observed Template:Chem2 and Template:Chem2 bond distances in the Template:Chem2 cation are 1.089(9) and 1.257(8) Å respectively, among the shortest experimentally observed N-N and N-F bonds.

References

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