Tetrabromonickelates
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The tetrabromonickelate anion contains a doubly-charged nickel atom (Ni2+) surrounded by four bromide ions in a tetrahedral arrangement. The formula is iBr4sup>2−. The anion combines with cations to form a series of salts called tetrabromonickelates. Strongly-coordinating solvents will displace one or more of the bromido ligands from the complex. Solvents that can dissolve tetrabromonickelate include acetone,
acetonitrile Acetonitrile, often abbreviated MeCN (methyl cyanide), is the chemical compound with the formula and structure . This colourless liquid is the simplest organic nitrile (hydrogen cyanide is a simpler nitrile, but the cyanide anion is not clas ...
,
methyl ethyl ketone Butanone, also known as methyl ethyl ketone (MEK), is an organic compound with the formula CH3C(O)CH2CH3. This colourless liquid ketone has a sharp, sweet odor reminiscent of acetone. It is produced industrially on a large scale, but occurs in nat ...
, and nitromethane. In the visible absorption spectrum there is a strong absorption band termed ''ν''3 near 710 nm which is caused by an electronic transition from 3T1(F) → 3T1(P). Another strong absorption in the near infrared called ''ν''2 near 770 nm is due to the 3T1(F) → 3A2(F) transition.


Salts

Dilithium tetrabromonickelate forms a dark blue solution in tetrahydrofuran. A mixture of lithium bromide and nickel bromide in water or methanol can transfer iBr4sup>2− ions into a cyclohexane-amine mixture. The solution formed is green. Tetraethylammonium tetrabromonickelate is blue. tetra-''n''-butylammonium tetrabromonickelate is purple blue in color, melting around 83°C. It is formed from nickel bromide and tetra-''n''-butylammonium bromide in ethyl alcohol. Tetraphenylphosphonium tetrabromonickelate(II) can be made from
nickel bromide Nickel(II) bromide is the name for the inorganic compounds with the chemical formula NiBr2(H2O)''x''. The value of ''x'' can be 0 for the anhydrous material, as well as 2, 3, or 6 for the three known hydrate forms. The anhydrous material is a yel ...
, triphenylphosphine, and bromobenzene by heating them together in a sealed tube at 250 °C. This substance is dark blue. If it is heated over 260° the color changes to green, and it melts at 273 °C. A dark blue oil, bis-(''o''-tolyltriethylphosphonium) tetrabromonickelate (o-CH3C6H6PEt3)2NiBr4 can be made from the reaction of ''o''-tolyl bis-triethylphosphine, nickel bromide and ''o''-tolyl bromide. (o-CH3OC6H6PEt3)2NiBr4 and (C6H5PEt3)2NiBr4 are made in a similar way. bis-(benzo 'e''1,3-dithiepan-2-diethylimmonium) tetrabromonickelate, abbreviated as (xdtc)2NiBr4, has dark blue crystals that melt at 166 °C. It is made from α,α'-dibromo-''o''-xylene and bis-(''N,N''-diethyldithiocarbamato)nickel(II) dissolved in 1,2-dichloroethane. bis-(tetra-''n''-butylphosphonium) tetrabromonickelate can form as a glass when nickel bromide is dissolved in molten tetra-''n''-butylphosphonium iodide. Blue 1,1,1-trimethylhydrazinium tetrabromonickelate 2NN(CH3)3sub>2NiBr4 is a salt stable between 70° and 260 °C. It can be formed by heating an octahedral neutral nickel complex where the trimethylhydrazinium and bromide are all ligands on a nickel atom. The salt decomposes at room temperature to polymeric trimethylhydrazinium nickel tribromide. The salt decomposes when dissolved in polar solvents, due to solvolysis.


Related

One bromine atom can be substituted by other ligands, such as triphenylphosphine, to make a dark green triphenylphosphinetribromonickelate ion. Analogous tetrahedral nickelates include
tetrafluoronickelate The fluoronickelates are a class of chemical compounds containing an anion with nickel at its core, surrounded by fluoride ions which act as ligands. This makes it a fluoroanion In chemistry, a fluoroanion or fluorometallate anion is a polyatomi ...
s,
tetrachloronickelates Tetrachloronickelate is the metal complex with the formula iCl4sup>2−. Salts of the complex are available with a variety of cations, but a common one is tetraethylammonium. When concentrated lithium chloride and nickel chloride solution in wa ...
,
tetraiodonickelates Tetraiodonickelate is a complex ion of nickel with four iodide atoms iI4sup>2− arranged in a tetrahedron. iI4sup>2− is red in solution. This colour is due to absorption around 530 nm and below 450 nm. Maximum light transmission is a ...
, and
tetracyanonickelate 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 c ...
s.


References

{{nickel compounds Nickel complexes Bromometallates