Silver hyponitrite

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Silver hyponitrite
Names
Other names
Silver(I) hyponitrite, Argentous hyponitrite
Identifiers
3D model (JSmol)
ChemSpider
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  • InChI=1S/2Ag.H2N2O2/c;;3-1-2-4/h;;(H,1,4)(H,2,3)/q2*+1;/p-2
    Key: WFHLUHLBCCOOIU-UHFFFAOYSA-L
  • N(=N[O-])[O-].[Ag+].[Ag+]
Properties
Ag2N2O2
Molar mass 275.75
Appearance bright canary yellow solid[1]
Density 5.75 g/cm3 (at 30 °C)
slightly soluble
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Silver hyponitrite is an ionic compound with formula Ag2N2O2 or (Ag+
)2[ON=NO]2−, containing monovalent silver cations and hyponitrite anions. It is a bright yellow solid practically insoluble in water and most organic solvents, including DMF and DMSO.[1][2][3]

Preparation

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The compound was described in 1848.[4]

The salt can be precipitated from a solution of sodium hyponitrite in water by the addition of silver nitrate:[2]

Na
2
N
2
O
2
+ 2 AgNO
3
Ag
2
N
2
O
2
+ 2 NaNO
3

Excess silver nitrate yields a brown or black precipitate.[1][2]

Silver hyponitrite can also be prepared by reacting silver nitrate with sodium amalgam.[5]

Properties and reactions

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Silver hyponitrite is sparingly soluble in concentrated alkali hyponitrite solutions, but quite soluble in aqueous ammonia due to the formation of the complex cation [(NH
3
)2Ag]+.[6] The compound is slowly decomposed by light.[5]

The anhydrous compound decomposes in vacuum at 158 °C. The primary decomposition products are silver(I) oxide Ag
2
O
and nitrous oxide N
2
O
. However, these then react to form a variable mixture of nitrogen, metallic silver, and various oxides of the two elements and silver salts.[1]

Hyponitrous acid

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Reaction of silver hyponitrite with anhydrous hydrogen chloride in ether is the standard way to prepare hyponitrous acid:

Ag
2
N
2
O
2
+ 2 HCl → H
2
N
2
O
2
+ 2 AgCl

Spectroscopic data indicate a trans configuration for the resulting acid.[7]

Alkyl halides

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Silver hyponitrite reacts with alkyl halides, to form alkyl hyponitrites. For example, reaction with methyl bromide yields the spontaneously explosive dimethyl hyponitrite:[2]

2 CH
3
Br
+ Ag
2
N
2
O
2
H
3
C
-O-N=N-O-CH
3
+ 2 AgBr

Other alkyl hyponitrites reported in the literature include those of ethyl,[8] benzyl,[9][10][11] and tert-butyl.[12][13][14]

References

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  1. ^ a b c d Trambaklal Mohanlal Oza, Rajnikant Hariprasad Thaker (1955), "The Thermal Decomposition of Silver Hyponitrite". Journal of the American Chemical society, volume 77, issue 19, pages 4976–4980. Lua error in Module:Citation/CS1/Configuration at line 2172: attempt to index field '?' (a nil value).
  2. ^ a b c d G. David Mendenhall (1974), "Convenient synthesis of silver hyponitrite". Journal of the American Chemical society, volume 96, issue 15, page 5000. Lua error in Module:Citation/CS1/Configuration at line 2172: attempt to index field '?' (a nil value).
  3. ^ Lua error in Module:Citation/CS1/Configuration at line 2172: attempt to index field '?' (a nil value).
  4. ^ (1848), "On the formation of hyponitrite of silver". Philosophical Magazine Series 3, XIII. Intelligence and miscellaneous articles, volume 33 (1848), issue 219, page 75. Lua error in Module:Citation/CS1/Configuration at line 2172: attempt to index field '?' (a nil value).
  5. ^ a b Masatsugu Sekiguchi, Michio Kobayashi, Hiroshi Minato (1974), "Reactions between Acyl Halides and Silver Hyponitrite". Bulletin of the Chemical Society of Japan, volume 45, issue 9, pages 2932-2934. Lua error in Module:Citation/CS1/Configuration at line 2172: attempt to index field '?' (a nil value).
  6. ^ C.N. Polydoropoulos, Th. Yannakopoulos (1961), "Silver hyponitrite: Solubility product and complexes in aqueous ammonia". Journal of Inorganic and Nuclear Chemistry, volume 19, issues 1–2, pages 107–114. Lua error in Module:Citation/CS1/Configuration at line 2172: attempt to index field '?' (a nil value).
  7. ^ Lua error in Module:Citation/CS1/Configuration at line 2172: attempt to index field '?' (a nil value).
  8. ^ J. R. Partington and C. C. Shah (1932), J. Chem. Soc., page 2589.
  9. ^ Lua error in Module:Citation/CS1/Configuration at line 2172: attempt to index field '?' (a nil value).
  10. ^ J. B. Sousa and S. K. Ho (1960), Nature, volume 186, page 776.
  11. ^ Lua error in Module:Citation/CS1/Configuration at line 2172: attempt to index field '?' (a nil value).
  12. ^ H. Kiefer and T. G. Traylor (1966), Tetrahedron Lett., page 6163.
  13. ^ Lua error in Module:Citation/CS1/Configuration at line 2172: attempt to index field '?' (a nil value).
  14. ^ R. C. Neuman and R. J. Bussey (1970), J. Am. Chem. Soc., volume 92, page 2440.