Chemistry:Tetrachloronickelate
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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.[1]
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When concentrated lithium chloride and nickel chloride solution in water is mixed, only a pentaaquachloro complex is formed: [Ni(H2O)5Cl]+. However in other organic solvents, or molten salts the tetrachloronickelate ion can form. Nickel can be separated from such a solution in water or methanol, by partitioning it into a cyclohexane solution of amines.[2]
Organic ammonium salts of the type (R3NH)2[NiCl4] are often thermochromic (R = Me, Et, Pr). Near room temperature, these salts are yellow , but these solids become blue when heated to near 70 °C. The bright blue color is characteristic of tetrahedral [NiCl4]2−, the intensity being a consequence of the Laporte selection rule. The yellow color results from a polymer consisting of octahedral Ni centers. The corresponding tetrabromonickelates are also thermochromic with a lower transition temperatures.[3]
History
The blue colour due to the tetrachloronickelate ion was first observed in 1944 when Remy and Meyer melted cesium chloride and cesium nickel trichloride together.[4]
Compounds
| formula | name | structure | Remarks | references |
|---|---|---|---|---|
| Cs2NiCl4 | cesium tetrachloronickelate | blue, stable only over 70° | [4] | |
| [(CH3)4N]2NiCl4 | Tetramethylammonium tetrachloronickelate | dark blue | [5] | |
| [(C2H5)4N]2NiCl4 | Tetraethylammonium tetrachloronickelate | [6][4] | ||
| [H2NN(CH3)3]2NiCl4 | 1,1,1-trimethylhydrazinium tetrachloronickelate | blue, only stable over 145 °C, under this is yellow | [7] | |
| [(C6H5)4As]2NiCl4 | bis-tetraphenylarsonium tetrachloronickelate | blue, melts at 199.5°C | [5] | |
| [(C6H5)3CH3As]2NiCl4 | bis-triphenylmethylarsonium tetrachloronickelate | blue | [4] | |
| [C2mim]2NiCl4 | 1-ethyl-3-methylimidazolium tetrachloronickelate(II) | tetragonal I41/a a=14.112 c=19.436 V=3871.1 Z=8 density=1.47 MW=422.84 | melts at 92° | [8][9] |
| [C4mim]2NiCl4 | 1-butyl-3-methylimidazolium tetrachloronickelate(II) | dark blue, melts at 56°C | [8] | |
| [C5mim]2NiCl4 | 1-pentyl-3-methylimidazolium tetrachloronickelate(II) | dark blue liquid | [8] | |
| [C6mim]2NiCl4 | 1-hexyl-3-methylimidazolium tetrachloronickelate(II) | dark blue liquid | [8] | |
| [C7mim]2NiCl4 | 1-heptyl-3-methylimidazolium tetrachloronickelate(II) | dark blue liquid | [8] | |
| [C8mim]2NiCl4 | 1-octyl-3-methylimidazolium tetrachloronickelate(II) | dark blue liquid | [8] | |
| [NH3CH2CH2NH3]NiCl4 | ethylenediammonium tetrachloronickelate(II) | perovskite layered, space group P21/c a=8.441, b=6.995, c=6.943, β=92.925 Z=2 | brown, isostructural with Mn, Cu, Pd, and Cd compounds | [10] |
Related substances
References
- ↑ Naida S. Gill; F. B. Taylor (1967). "Tetrahalo Complexes of Dipositive Metals in the First Transition Series". Inorganic Syntheses. 9. pp. 136–142. doi:10.1002/9780470132401.ch37. ISBN 978-0-470-13240-1.
- ↑ 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.
- ↑ Ferraro, John R.; Sheren, Anne T. (3 February 1978). "Some new thermochromic complexes of Nickel(II) of the type [R/sub x/NH/sub 4-x/]2NiCl4". Inorganic Chemistry 17 (9): 2498–2502. doi:10.1021/ic50187a032.
- ↑ 4.0 4.1 4.2 4.3 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.
- ↑ 5.0 5.1 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.
- ↑ 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.
- ↑ 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.
- ↑ 8.0 8.1 8.2 8.3 8.4 8.5 Meredith, M. Brett; McMillen, C. Heather; Goodman, Jonathan T.; Hanusa, Timothy P. (August 2009). "Ambient temperature imidazolium-based ionic liquids with tetrachloronickelate(II) anions". Polyhedron 28 (12): 2355–2358. doi:10.1016/j.poly.2009.04.037.
- ↑ Hitchcock, Peter B.; Seddon, Kenneth R.; Welton, Thomas (1993). "Hydrogen-bond acceptor abilities of tetrachlorometalate(II) complexes in ionic liquids". Journal of the Chemical Society, Dalton Transactions (17): 2639. doi:10.1039/DT9930002639.
- ↑ Skaarup, Steen; Berg, Rolf Willestofte (September 1978). "Structural properties and vibrational spectra of the ethylene-diammonium family of perovskite layer-type crystals: [NH3CH2CH2NH3] [MCl4], M = Ni, Pd, Cu, Cd, Mn". Journal of Solid State Chemistry 26 (1): 59–67. doi:10.1016/0022-4596(78)90133-0. Bibcode: 1978JSSCh..26...59S.
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