Nickel(II) nitrite
| Names | |
|---|---|
| IUPAC name
Nickel(II) nitrite | |
| Other names
nickel dinitrite | |
| Identifiers | |
| 17861-62-0 | |
| 3D model (Jmol) | Interactive image |
| ChemSpider | 20127081 |
| PubChem | 20831815 |
| RTECS number | RA1080000 |
| UN number | 2726 |
| |
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| Properties | |
| Ni(NO2)2 | |
| Molar mass | 150.73 g/mol |
| Appearance | blue-green crystals |
| Density | 8.90 g/cm3 (20 °C) |
| very soluble | |
| Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). | |
| Infobox references | |
Nickel(II) nitrite is an inorganic compound with the chemical formula Ni(NO2)2 [1] Anhydrous nickel nitrite was first discovered by Cyril Clifford Addison on 1961. He allowed gaseous nickel tetracarbonyl to react with dinitrogen tetroxide, yielding a green smoke. Nickel nitrite was the second transition element anhydrous nitrite discovered after silver nitrite.[2] Nickel nitrite decomposes when heated to 220°, however it can be heated up to 260° in argon. The nitrite is covalently bonded to nickel, and the material is slightly volatile.[3] The infrared spectrum of the solid has absorption bands at 1575, 1388, 1333, 1240, 1080, and 830 cm−1.[3] liquid dinitrogentetroxide oxidises nickel nitrite to nickel nitrate.[3]
Double salts
The nitronickelates are related compounds where more nitro groups are attached to nickel to yield an anion. They could be described as nickel double nitrites.
Solution
In water when nickel nitrite dissolves, different mixed nitro-aqua complexes form such as Ni(NO2)2(H2O)4, Ni(NO2)3(H2O)3−, and Ni(NO2)(H2O)5+.[4] The aqueous complex Ni(NO2)2(H2O)4 forms when an alkali metal nitrite is added to a nickel salt solution. The complex is a much more intense emerald green colour than the Ni(H2O)62+ ion. The equilibrium constant Ni(H2O)62+ + 2NO2– ⇌ Ni(NO2)2(H2O)4 + 2H2O is 0.16 at standard conditions. Brooker claims that intense light photocatalyses the destruction of the ionic nitro complexes, leaving only Ni(NO2)2(H2O)4.[4]
Nickel nitrite slowly decomposes slightly in aqueous solution due to disproportionation. 3NO2− + 2H+ → 2NO(g) + NO3– +H2O.[4]
Complexes
Nickel nitrite can also form complexes with other ligands. In some of these the nitro groups are altered in their attachment to nickel, so that instead of linking via a nitrogen atom, they link via an oxygen atom. This is then called "nitrito". The change to nitrito happens because the other ligands are bulky, causing steric hindrance, so they get in the way. These complexes can be stable as solids. Members include the blue Ni(pyridine)4(ONO)2, blue green Ni(substituted ethylene diamines)2(ONO)2, blue Ni(N,N-diethylethylenediamine)2(NO2)2, blue-green Ni(N,N'-diethylethylenediamine)2(NO2)2, red Ni(NO2)2(NH3)4, red Ni(ethylenediamine)2(NO2)2, red Ni(N-monosubstituted-ethylenediamine)2(NO2)2,[5] red Ni(1,2-diamino-2-methylpropane)2(NO2)2, pink Ni(N-methylethylenediamine)2(NO2)2, red Ni(N-ethylethylenediamine)2(NO2)2, red Ni(rac-diphenylethylenediamine)2(NO2)2.[6] In a chloroform solution some of these nitro- complexes partially change into nitito- complexes. This is called linkage isomerism.[6] Yet more complexed nickel nitrites include red Ni(2-(aminomethyl)piperidine)2(NO2)2, reddish blue-violet Ni(2-(aminomethyl)pyridine)2(NO2)2, violet Ni(2-(methylaminomethyl)pyridine)2(ONO)2, blue Ni(2-(methylaminomethyl)piperidine)2(ONO)2, blue Ni(2-(aminomethyl)-6-methylpyridine)2(ONO)2, blue-grey Ni(2-(aminomethyl)-6-methylpiperidine)2(ONO)2,[7] red Ni(N,N'-dimethylethylenediamine)2(NO2)2•H2O, Ni(N,N-dimethylethylenediamine)2(NO2)2,[8] green Ni(α-picoline)2(NO2)2, green Ni(quinoline)2(NO2)2,[9]
References
- ↑ University of Akron Chemical Database
- ↑ Lord Lewis of Newnham; Johnson, B. F. G. (1 November 1997). "Cyril Clifford Addison. 28 November 1913--1 April 1994.: Elected F.R.S. 1970". Biographical Memoirs of Fellows of the Royal Society. 43 (0): 3–12. doi:10.1098/rsbm.1997.0001. JSTOR 770322.
- 1 2 3 Addison, C. C.; Johnson, B. F. G; Logan, N.; Wojcicki, A. (August 1961). "Transition-metal Nitrites". Proceedings of the Chemical Society (August): 306–307. doi:10.1039/PS9610000273.
- 1 2 3 Brooker, M. H. (1975). "Infra-red and Raman spectral study of the aqueous nickel(II)–nitrite system. Evidence for photochemical alteration of the chemical equilibrium". Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases. 71 (0): 647. doi:10.1039/F19757100647.
- ↑ Goodgame, D. M. L.; Hitchman, M. A. (October 1964). "Studies of Nitro and Nitrito Complexes. I. Some Nitrito Complexes of Nickel(II)". Inorganic Chemistry. 3 (10): 1389–1394. doi:10.1021/ic50020a010.
- 1 2 Goodgame, D. M. L.; Hitchman, M. A. (August 1966). "Studies of Nitro and Nitrito Complexes. III. Some Nitro Complexes of Nickel(II) and a Nitro-Nitrito Equilibrium". Inorganic Chemistry. 5 (8): 1303–1307. doi:10.1021/ic50042a001.
- ↑ El-Sayed, Laila; Ragsdale, Ronald O. (September 1967). "Nickel(II) nitrite complexes". Inorganic Chemistry. 6 (9): 1640–1643. doi:10.1021/ic50055a006.
- ↑ Finney, AJ; Hitchman, MA; Raston, CL (1981). "Structural and spectroscopic studies of transition metal nitrite complexes. I. Crystal structures and spectra of trans-Bis(ethane- 1,2 diamine)dinitronickel(II), trans-Bis[N, N-dimethyl(ethane- 1,2-diamine)]dinitritonickel(II) and trans-bis[N,N'-dimethyl(ethane-1,2 diamine)]dinitronickel(II) monohydrate". Australian Journal of Chemistry. 34 (10): 2047. doi:10.1071/CH9812047.
- ↑ Goodgame, D. M. L.; Hitchman, M. A. (May 1965). "Studies of Nitro and Nitrito Complexes. II. Complexes Containing Chelating NO2 Groups". Inorganic Chemistry. 4 (5): 721–725. doi:10.1021/ic50027a027.