Nickel(II) nitrite

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Nickel(II) nitrite
Names
IUPAC name
Nickel(II) nitrite
Other names
nickel dinitrite
Identifiers
3D model (JSmol)
ChemSpider
PubChem CID
RTECS number
  • RA1080000
UN number 2726
  • InChI=1S/2HNO2.Ni/c2*2-1-3;/h2*(H,2,3);/q;;+2/p-2
    Key: ZVHHIDVFSYXCEW-UHFFFAOYSA-L
  • N(=O)[O-].N(=O)[O-].[Ni+2]
Properties
Ni(NO2)2
Molar mass 150.73 g/mol
Appearanceblue-green crystals
Density 8.90 g/cm3 (20 °C)[ dubious ]
very soluble
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Nickel(II) nitrite is an inorganic compound with the chemical formula Ni(NO2)2. [1] Anhydrous nickel nitrite was first discovered in 1961 by Cyril Clifford Addison, who 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]

Contents

Properties

Nickel nitrite decomposes when heated to 220°C, however it can be heated up to 260°C 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 dinitrogen tetroxide oxidises nickel nitrite to nickel nitrate. [3]

In solution

When nickel nitrite dissolves in water, 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:

Ni(H2O)2+6 + 2 NO2 Ni(NO2)2(H2O)4 + 2 H2O; K = 0.16 at standard conditions

The complex is a much more intense emerald green colour than the Ni(H2O)62+ ion. 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: [4]

3 NO2 + 2 H+ → 2 NO(g) + NO3 + H2O

Complexes

In the presence of additional ligands, nickel nitrite can change colors substantially. These color changes may arise from the new molecular orbitals, or linkage isomerism, in which the nitro ligands rearrange to a nitrito (-ONO) complex. Sorted by color, known compounds include: [5] [6] [7]

Violet
Reddish blue-violet
Blue-gray
Blue
Blue-green
Green
Red
Pink

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.

Related Research Articles

The nitrite ion has the chemical formula NO
2
. Nitrite is widely used throughout chemical and pharmaceutical industries. The nitrite anion is a pervasive intermediate in the nitrogen cycle in nature. The name nitrite also refers to organic compounds having the –ONO group, which are esters of nitrous acid.

<span class="mw-page-title-main">Nitro compound</span> Organic compound containing an −NO₂ group

In organic chemistry, nitro compounds are organic compounds that contain one or more nitro functional groups. The nitro group is one of the most common explosophores used globally. The nitro group is also strongly electron-withdrawing. Because of this property, C−H bonds alpha (adjacent) to the nitro group can be acidic. For similar reasons, the presence of nitro groups in aromatic compounds retards electrophilic aromatic substitution but facilitates nucleophilic aromatic substitution. Nitro groups are rarely found in nature. They are almost invariably produced by nitration reactions starting with nitric acid.

<span class="mw-page-title-main">Nickel(II) chloride</span> Chemical compound

Nickel(II) chloride (or just nickel chloride) is the chemical compound NiCl2. The anhydrous salt is yellow, but the more familiar hydrate NiCl2·6H2O is green. Nickel(II) chloride, in various forms, is the most important source of nickel for chemical synthesis. The nickel chlorides are deliquescent, absorbing moisture from the air to form a solution. Nickel salts have been shown to be carcinogenic to the lungs and nasal passages in cases of long-term inhalation exposure.

In chemistry, linkage isomerism or ambidentate isomerism is a form of isomerism in which certain coordination compounds have the same composition but differ in their metal atom's connectivity to a ligand.

<span class="mw-page-title-main">Hapticity</span> Number of contiguous atoms in a ligand that bond to the central atom in a coordination complex

In coordination chemistry, hapticity is the coordination of a ligand to a metal center via an uninterrupted and contiguous series of atoms. The hapticity of a ligand is described with the Greek letter η ('eta'). For example, η2 describes a ligand that coordinates through 2 contiguous atoms. In general the η-notation only applies when multiple atoms are coordinated. In addition, if the ligand coordinates through multiple atoms that are not contiguous then this is considered denticity, and the κ-notation is used once again. When naming complexes care should be taken not to confuse η with μ ('mu'), which relates to bridging ligands.

<span class="mw-page-title-main">Diphenylethylenediamine</span> Chemical compound

1,2-Diphenyl-1,2-ethylenediamine, DPEN, is an organic compound with the formula H2NCHPhCHPhNH2, where Ph is phenyl (C6H5). DPEN exists as three stereoisomers: meso and two enantiomers S,S- and R,R-. The chiral diastereomers are used in asymmetric hydrogenation. Both diastereomers are bidentate ligands.

<span class="mw-page-title-main">1,2-Bis(dimethylphosphino)ethane</span> Chemical compound

1,2-Bis(dimethylphosphino)ethane (dmpe) is a diphosphine ligand in coordination chemistry. It is a colorless, air-sensitive liquid that is soluble in organic solvents. With the formula (CH2PMe2)2, dmpe is used as a compact strongly basic spectator ligand (Me = methyl), Representative complexes include V(dmpe)2(BH4)2, Mn(dmpe)2(AlH4)2, Tc(dmpe)2(CO)2Cl, and Ni(dmpe)Cl2.

<span class="mw-page-title-main">Nickel(II) bis(acetylacetonate)</span> Coordination complex

Nickel(II) bis(acetylacetonate) is a coordination complex with the formula [Ni(acac)2]3, where acac is the anion C5H7O2 derived from deprotonation of acetylacetone. It is a dark green paramagnetic solid that is soluble in organic solvents such as toluene. It reacts with water to give the blue-green diaquo complex Ni(acac)2(H2O)2.

<span class="mw-page-title-main">Dichloro(1,3-bis(diphenylphosphino)propane)nickel</span> Chemical compound

Dichloro[1,3-bis(diphenylphosphino)propane]nickel a coordination complex with the formula NiCl2(dppp); where dppp is the diphosphine 1,3-bis(diphenylphosphino)propane. It is used as a catalyst in organic synthesis. The compound is a bright orange-red crystalline powder.

<span class="mw-page-title-main">Nitropentaamminecobalt(III) chloride</span> Chemical compound

Nitropentaamminecobalt(III) chloride is an inorganic compound with the molecular formula [Co(NH3)5(NO2)]Cl2. It is an orange solid that is soluble in water. Although it has no applications, the compound has been of academic interest as a source of the transition metal nitrite complex [Co(NH3)5(NO2)]2+.

<span class="mw-page-title-main">Cyanonickelate</span> Class of chemical compounds

The cyanonickelates are a class of chemical compound containing anions consisting of nickel atoms, and cyanide groups. The most important of these are the tetracyanonickelates containing four cyanide groups per nickel. The tetracyanonickelates contain the [Ni(CN)4]2− anion. This can exist in solution or in solid salts. The ion has cyanide groups arranged in a square around the central nickel ion. The symmetry of the ion is D4h. The distance from the nickel atom to the carbon is 1.87 Å, and the carbon-nitrogen distance is 1.16 Å. Tetracyanonickelate(II) can be oxidised electrochemically in solution to yield tetracyanonickelate(III) [Ni(CN)4]. [Ni(CN)4] is unstable and Ni(III) oxidises the cyanide to cyanate OCN. Tetracyanonickelate(III) can add two more cyanide groups to form hexacyanonickelate(III).

<span class="mw-page-title-main">Tetrachloronickelate</span> Class of chemical compounds

Tetrachloronickelate is the metal complex with the formula [NiCl4]2−. Salts of the complex are available with a variety of cations, but a common one is tetraethylammonium.

Nickel compounds are chemical compounds containing the element nickel which is a member of the group 10 of the periodic table. Most compounds in the group have an oxidation state of +2. Nickel is classified as a transition metal with nickel(II) having much chemical behaviour in common with iron(II) and cobalt(II). Many salts of nickel(II) are isomorphous with salts of magnesium due to the ionic radii of the cations being almost the same. Nickel forms many coordination complexes. Nickel tetracarbonyl was the first pure metal carbonyl produced, and is unusual in its volatility. Metalloproteins containing nickel are found in biological systems.

The nitronickelates are a class of chemical compounds containing a nickel atom complexed by nitro groups, -NO2. Nickel can be in a +2 or +3 oxidation state. There can be five (pentanitronickelates), or six, (hexanitronickelates) nitro groups per nickel atom. They can be considered the double nitrites of nickel nitrite.

The tetrabromonickelate anion contains a doubly-charged nickel atom (Ni2+) surrounded by four bromide ions in a tetrahedral arrangement. The formula is [NiBr4]2−.

<span class="mw-page-title-main">1,4-Bis(diphenylphosphino)butane</span> Chemical compound

1,4-Bis(diphenylphosphino)butane (dppb) is an organophosphorus compound with the formula (Ph2PCH2CH2)2. It is less commonly used in coordination chemistry than other diphosphine ligands such as dppe. It is a white solid that is soluble in organic solvents.

<span class="mw-page-title-main">Dichloro(1,2-bis(diphenylphosphino)ethane)nickel</span> Chemical compound

Dichloro[1,2-bis(diphenylphosphino)ethane]nickel is a coordination complex with the formula NiCl2(dppe); where dppe is the diphosphine 1,2-bis(diphenylphosphino)ethane. It is used as a reagent and as a catalyst. The compound is a bright orange-red diamagnetic solid. The complex adopts a square planar geometry.

<span class="mw-page-title-main">Transition metal dithiocarbamate complexes</span>

Transition metal dithiocarbamate complexes are coordination complexes containing one or more dithiocarbamate ligand, which are typically abbreviated R2dtc. Many complexes are known. Several homoleptic derivatives have the formula M(R2dtc)n where n = 2 and 3.

<span class="mw-page-title-main">Transition metal nitrite complex</span> Chemical complexes containing one or more –NO₂ ligands

In organometallic chemistry, transition metal complexes of nitrite describes families of coordination complexes containing one or more nitrite ligands. Although the synthetic derivatives are only of scholarly interest, metal-nitrite complexes occur in several enzymes that participate in the nitrogen cycle.

<span class="mw-page-title-main">Transition metal nitrate complex</span> Compound of nitrate ligands

A transition metal nitrate complex is a coordination compound containing one or more nitrate ligands. Such complexes are common starting reagents for the preparation of other compounds.

References

  1. University of Akron Chemical Database Archived 2012-12-15 at archive.today
  2. 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: 3–12. doi:10.1098/rsbm.1997.0001. JSTOR   770322. S2CID   70964112.
  3. 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.
  4. 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: 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.
    • 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.
    • 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.
  5. El-Sayed, Laila; Ragsdale, Ronald O. (September 1967). "Nickel(II) nitrite complexes". Inorganic Chemistry. 6 (9): 1640–1643. doi:10.1021/ic50055a006.
  6. 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.