Tetrabromonickelate

The tetrabromonickelate is an anion containing a doubly positive charged nickel atom (Ni2+) surrounded by four bromide ions in a tetrahedral shape. The formula is [NiBr4]2−.

The anion combines with cations to form a series of salts called tetrabromonickelates. Strongly coordinating or polar solvents will add solvent molecules displacing the bromine in the complex.[1] Solvents that can dissolve tetrabromonickelate include acetone, acetonitrile, methyl ethyl ketone, and nitromethane.[2]

In visible light there is a strong absorption band termed ν3 near 710 nm which is caused by an electronic transition from 3T1(F) → 3T1(P). Another strong absorption and is in the near infrared called ν2 near 770 nm due to 3T1(F) → 3A2(F).[2]

Salts

Dilithium tetrabromonickelate forms a dark blue solution in tetrahydrofuran.[3] A mixture of lithium bromide and nickel bromide in water or methanol can transfer NiBr4 ions into a cyclohexane-amine mixture. The solution formed is green.[4]

Tetraethylammonium tetrabromonickelate[5] is blue.[6]

tetra-n-butylammonium tetrabromonickelate is purple blue in colour melting around 83°. It is formed from nickel bromide and tetra-n-butylammonium bromide in ethyl alcohol.[7]

Tetraphenylphosphonium tetrabromonickelate(II)[1] can be made from nickel bromide, 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 colour changes to green, and it melts at 273 °C.[8]

A dark blue oil, bis-(o-tolyltriethylphosphonium) tetrabromonickelate (o-CH3C6H6PEt3)2NiBr4 can be made from the reaction of o-tolyl bis-triethylphosphine nickelbromide with o-tolyl bromide. (o-CH3OC6H6PEt3)2NiBr4 and (C6H5PEt3)2NiBr4 are made in a similar way.[9]

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.[10]

bis-(tetra-n-butylphosphonium) tetrabromonickelate can form as a glass with nickel bromide is dissolved in molten tetra-n-butylphosphonium iodide.[11]

Blue 1,1,1-trimethylhydrazinium tetrabromonickelate [H2NN(CH3)3]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 decomposed by polar solvents, due to solvation of the nickel atom where the solvent molecules replace the bromide.[12]

One bromine atom can be substituted by other ligands such as triphenylphosphine to make a dark green triphenylphosphinetribromonickelate ion.[8] Analogous tetrahedral nickelates include tetrafluoronickelates, tetrachloronickelates, tetraiodonickelates, and tetracyanonickelates.

References

  1. 1 2 Goodgame, D. M. L.; Goodgame, M.; Cotton, F. A. (October 1961). "Electronic Spectra of Some Tetrahedral Nickel(II) Complexes". Journal of the American Chemical Society. 83 (20): 4161–4167. doi:10.1021/ja01481a014.
  2. 1 2 Fine, Dwight A. (March 1965). "Tetrahedral Bromide Complexes of Nickel(II) in Organic Solvents". Inorganic Chemistry. 4 (3): 345–350. doi:10.1021/ic50025a019.
  3. ↑ Fertel, Lawrence B. (15 April 2001). "Dilithium Tetrabromonickelate(II)". e-EROS Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rd267.
  4. ↑ Florence, T. M.; Farrar, Yvonne J. (July 1968). "Liquid-liquid extraction of nickel with long-chain amines from aqueous and nonaqueous halide media". Analytical Chemistry. 40 (8): 1200–1206. doi:10.1021/ac60264a010.
  5. ↑ Inman, Guy W.; Hatfield, William E.; Jones, Edwin R. (August 1971). "The magnetic properties of tetraethylammonium tetrachloronickelate(II) and tetraethylammonium tetrabromonickelate(II)". Inorganic and Nuclear Chemistry Letters. 7 (8): 721–723. doi:10.1016/0020-1650(71)80078-8.
  6. ↑ Gill, Naida S.; Nyholm, R. S. (1959). "802. Complex halides of the transition metals. Part I. Tetrahedral nickel complexes". Journal of the Chemical Society (Resumed): 3997. doi:10.1039/JR9590003997.
  7. ↑ Smith, G. Pedro.; Liu, C. H.; Griffiths, Trevor R. (November 1964). "Charge-Transfer and Ligand-Field Spectra of Tetrahedral Tetrahalonickel(II) Ions in Molten Dimethyl Sulfone and Molten Organic Halide Salts". Journal of the American Chemical Society. 86 (22): 4796–4802. doi:10.1021/ja01076a014.
  8. 1 2 Cotton, F. A.; Faut, O. D.; Goodgame, D. M. L. (January 1961). "Preparation, Spectra and Electronic Structures of Tetrahedral Nickel(II) Complexes Containing Triphenylphosphine and Halide Ions as Ligands". Journal of the American Chemical Society. 83 (2): 344–351. doi:10.1021/ja01463a021.
  9. ↑ Tsou, T. T.; Kochi, J. K. (December 1979). "Mechanism of biaryl synthesis with nickel complexes". Journal of the American Chemical Society. 101 (25): 7547–7560. doi:10.1021/ja00519a015.
  10. ↑ Previdi, John C.; Krause, Ronald A. (February 1976). "Ligand alkylation of bis(N,N-diethyldithiocarbamato) nickel(II) by α,α'-dibromo-o-xylene". Inorganic Chemistry. 15 (2): 462–464. doi:10.1021/ic50156a044.
  11. ↑ Islam, N.; Islam, M. R.; Ahmad, S.; Waris, B. (May 1975). "Optical spectra and the free-volume model for the transport behavior of glass-forming melts". Journal of the American Chemical Society. 97 (11): 3026–3032. doi:10.1021/ja00844a018.
  12. ↑ Goedken, V. L.; Vallarino, L. M.; Quagliano, J. V. (December 1971). "Cationic ligands. Coordination of the 1,1,1-trimethylhydrazinium cation to nickel(II)". Inorganic Chemistry. 10 (12): 2682–2685. doi:10.1021/ic50106a011.
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