Angeli's salt

Last updated
Angeli's salt
Angeli's salt.svg
Identifiers
3D model (JSmol)
PubChem CID
UNII
  • InChI=1S/N2O3.2Na/c3-1-2(4)5;;/q;2*+1
    Key: XDPWLJKQGUTUKZ-UHFFFAOYSA-N
  • N(=O)[N+](=O)[O-].[Na+].[Na+]
Properties
N2Na2O3
Molar mass 121.991 g·mol−1
Appearancewhite solid
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Angeli's salt, sodium trioxodinitrate, is the inorganic compound with the formula Na2[N2O3]. It contains nitrogen in an unusual reduced state. It is a colorless, water-soluble solid, hence a salt. In research, this salt is used as a source of the metastable nitroxyl (HNO), which is a signalling molecule in nature. [1] It is also known by the name sodium trioxodinitrate(II) monohydrate.

Preparation and properties

As first reported by Angelo Angeli in 1896, the salt is prepared by combining hydroxylamine and an organic nitrate, as a source of nitronium (NO+
2
): [2] [3]

NH2OH + RONO2 + 2 NaOR′ → ROH + 2 R′OH + Na2N2O3

The structure of the hydrate has been confirmed by X-ray crystallography. The anion is planar. Starting from the ONN end, the bond distances are 1.35 Å (N−O), 1.26 Å (N−N), 1.31 Å (N−O), and 1.32 Å (N−-O). The negative charge is on the oxygen atoms at opposite ends of the molecule. The angles are 112.9° (Osingle−N−N), 118.4° (N−N−Otrans), and 122.5° (N−N−Ocis). This means that the nitrogen–nitrogen bond is a double bond, and that the cis oxygen is slightly repelled by the single oxygen. [4]

Reaction of Angeli's salt with secondary amines in the presence of a proton source results in extrusion of N2 via isodiazenes as proposed intermediates. [5]

Related Research Articles

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<span class="mw-page-title-main">Inorganic chemistry</span> Field of chemistry

Inorganic chemistry deals with synthesis and behavior of inorganic and organometallic compounds. This field covers chemical compounds that are not carbon-based, which are the subjects of organic chemistry. The distinction between the two disciplines is far from absolute, as there is much overlap in the subdiscipline of organometallic chemistry. It has applications in every aspect of the chemical industry, including catalysis, materials science, pigments, surfactants, coatings, medications, fuels, and agriculture.

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Angelo Angeli was an Italian chemist. Angeli's salt and the Angeli–Rimini reaction are named after him.

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References

  1. Nakagawa, H. (2013). "Controlled release of HNO from chemical donors for biological applications". J. Inorg. Biochem. 118: 187–190. doi:10.1016/j.jinorgbio.2012.10.004. PMID   23140899.
  2. Angeli, A. (1896). "Sopra la nitroidrossilammina" [On nitrohydroxylamine]. Gazz. Chim. Ital. (in Italian). 26: 17–28.
  3. Hughes, Martin N.; Cammack, Richard (1999). "Synthesis, chemistry, and Applications of Nitroxyl Ion Releasers Sodium Trioxodinitrate or Angeli's Salt and Piloty's Acid". Nitric Oxide, Part C: Biological and Antioxidant Activities. Methods in Enzymology. Vol. 301. pp. 279–287. doi:10.1016/S0076-6879(99)01092-7. ISBN   9780121822026. PMID   9919577.
  4. Hope, Hakon; Sequeira, Michael R. (February 1973). "Angeli's salt. Crystal structure of sodium trioxodinitrate(II) monohydrate, Na2N2O3·H2O". Inorganic Chemistry. 12 (2): 286–288. doi:10.1021/ic50120a008.
  5. Carey, Francis A.; Sundberg, Richard J. (2007). Advanced Organic Chemistry. Part B: Reactions and Synthesis (5th ed.). New York, NY: Springer. ISBN   9781601195494. OCLC   223941000.