Hyponitrite

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Hyponitrite
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In chemistry, hyponitrite may refer to the anion Template:Chem/link ([ON=NO]2−), or to any ionic compound that contains it. In organic chemistry, it may also refer to the group −O−N=N−O−, or any organic compound with the generic formula R1−O−N=N−O−R2, where R1 and R2 are organic groups.[1] Such compounds can be viewed as salts and esters of hyponitrous acid. An acid hyponitrite is an ionic compound with the anion Template:Chem/link ([HON=NO]).

Hyponitrite ion

Hyponitrite exhibits cis–trans isomerism.[2]

The trans (E) form is generally found in hyponitrite salts such as sodium hyponitrite (Template:Chem/link) and silver(I) hyponitrite (Template:Chem/link).

The cis (Z) form of sodium hyponitrite can be obtained too, but it is more reactive than the trans form.[2] The cis hyponitrite anion is nearly planar and almost symmetric, with lengths of about 140 pm for N−O bond and 120 pm for the N−N bond, and O−N−N angles of about 119°.[3]

Reactions

The hyponitrite ions can act as a bidentate ligand in either bridging or chelating mode. There is a bridging cis-hyponitrite group in the red dinuclear form of nitrosyl pentammine cobalt(III) chloride, [Co(NH3)5NO]Cl2.[4]

Hyponitrite can reduce elemental iodine to hydroiodic acid:[4]

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Hyponitrite esters

Organic trans-hyponitrites R1−O−N=N−O−R2 can be obtained by reacting trans silver(I) hyponitrite Template:Chem/link with various alkyl halides. For example, reaction with tert-butyl chloride yields trans di-tert-butyl hyponitrite.[5][6][7][8]

Other alkyl radicals reported in the literature include ethyl,[9] and benzyl.[10][11][12] These compounds can be a source of alkoxyl radicals.[13]

See also

Other nitrogen oxyanions include

References

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  2. a b Egon Wiberg, Arnold Frederick Holleman (2001) Inorganic Chemistry, Elsevier Template:ISBN
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