四氯镍酸根

四氯镍酸根离子是一种金属配合物,化学式为[NiCl4]2−,其盐称作四氯镍酸盐。四氯镍酸根离子可以与各种各样的阳离子键合,但常见的包括四乙基铵阳离子[1]

四面体四氯镍酸络离子
(Et4N)2NiCl4样品。

当浓氯化锂和氯化镍的水溶液混合在一起时,它们只会形成五水氯络合物:[Ni(H2O)5Cl]+。然而,在其他有机溶剂或熔融的盐中,它们可以形成四氯镍酸根离子。如果将镍配分到胺的环己烷溶液中,镍就可以从这些盐的水或甲醇溶液中被分离出来。[2]

(R3NH)2[NiCl4]之类的有机铵盐通常可以发生热致变色(R = Me, Et, Pr)。在近室温的环境下,这些盐呈黄色,但它们在70 °C下会变成蓝色。亮蓝色是四面体的[NiCl4]2−的特征,而强度是拉波特规则导致的。盐呈黄色是因为它们生成了由八面体Ni中心组成的聚合物。相应的四溴镍酸盐在较低的温度下也会发生热致变色的。[3]

历史

1944年,Remy和Meyer将氯化铯和三氯化铯镍一起熔化时,首次观察到由四氯镍酸根离子引起的蓝色。[4]

化合物

公式 名称 结构 备注 参考
Cs2NiCl4 四氯镍酸铯 只在超过70 °C的环境下保持蓝色 [4]
[(CH3)4N]2NiCl4 四甲基四氯镍酸铵 深蓝色 [5]
[(C2H5)4N]2NiCl4 四乙基四氯镍酸铵英语Tetraethylammonium tetrachloronickelate [6] [4]
[H2NN(CH3)3]2NiCl4 1,1,1-三甲基肼正离子四氯镍盐(1,1,1-三甲基四氯镍酸𰽟) 只在超过145 °C的环境下保持蓝色,在此温度以下呈黄色 [7]
[(C6H5)4As]2NiCl4 双四苯基砷正离子(鎓)四氯镍酸盐 蓝色,熔点199.5 °C [5]
[(C6H5)3CH3As]2NiCl4 双三苯甲基砷正离子(鎓)四氯镍酸盐 蓝色 [4]
[C2mim]2NiCl4 1-乙基-3-甲基咪唑正离子(鎓)四氯镍(II)酸盐 四方晶系,I41/a
a=14.112,c=19.436,V=3871.1,Z=8,密度=1.47,MW=422.84
熔点92 °C [8] [9]
[C4mim]2NiCl4 1-丁基-3-甲基咪唑正离子(鎓)四氯镍(II)酸盐 深蓝色,熔点56 °C [8]
[C5mim]2NiCl4 1-戊基-3-甲基咪唑正离子(鎓)四氯镍(II)酸盐 深蓝色液体 [8]
[C6mim]2NiCl4 1-己基-3-甲基咪唑正离子(鎓)四氯镍(II)酸盐 深蓝色液体 [8]
[C7mim]2NiCl4 1-庚基-3-甲基咪唑正离子(鎓)四氯镍(II)酸盐 深蓝色液体 [8]
[C8mim]2NiCl4 1-辛基-3-甲基咪唑正离子(鎓)四氯镍(II)酸盐 深蓝色液体 [8]
[NH3CH2CH2NH3]NiCl4 乙二胺正离子四氯镍(II)酸盐 钙钛矿层状,空间群P21/c
a=8.441,b=6.995,c=6.943,β=92.925,Z=2
棕色,与Mn、Cu、Pd和Cd化合物同构 [10]

有关物质

参考文献

  1. ^ Naida S. Gill; F. B. Taylor. Tetrahalo Complexes of Dipositive Metals in the First Transition Series. Inorganic Syntheses 9. 1967: 136–142. ISBN 978-0-470-13240-1. doi:10.1002/9780470132401.ch37. 
  2. ^ Florence, T. M.; Farrar, Yvonne J. Liquid-liquid extraction of nickel with long-chain amines from aqueous and nonaqueous halide media. Analytical Chemistry. July 1968, 40 (8): 1200–1206. doi:10.1021/ac60264a010. 
  3. ^ Ferraro, John R.; Sheren, Anne T. Some new thermochromic complexes of Nickel(II) of the type [R/sub x/NH/sub 4-x/]2NiCl4. Inorganic Chemistry. 3 February 1978, 17 (9): 2498–2502. doi:10.1021/ic50187a032. 
  4. ^ 4.0 4.1 4.2 4.3 Gill, Naida S.; Nyholm, R. S. 802. Complex halides of the transition metals. Part I. Tetrahedral nickel complexes. Journal of the Chemical Society (Resumed). 1959: 3997. doi:10.1039/JR9590003997. 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. ^ 5.0 5.1 Cotton, F. A.; Faut, O. D.; Goodgame, D. M. L. Preparation, Spectra and Electronic Structures of Tetrahedral Nickel(II) Complexes Containing Triphenylphosphine and Halide Ions as Ligands. Journal of the American Chemical Society. January 1961, 83 (2): 344–351. doi:10.1021/ja01463a021. 
  6. ^ Inman, Guy W.; Hatfield, William E.; Jones, Edwin R. The magnetic properties of tetraethylammonium tetrachloronickelate(II) and tetraethylammonium tetrabromonickelate(II). Inorganic and Nuclear Chemistry Letters. August 1971, 7 (8): 721–723. doi:10.1016/0020-1650(71)80078-8. 
  7. ^ Goedken, V. L.; Vallarino, L. M.; Quagliano, J. V. Cationic ligands. Coordination of the 1,1,1-trimethylhydrazinium cation to nickel(II). Inorganic Chemistry. December 1971, 10 (12): 2682–2685. doi:10.1021/ic50106a011. 
  8. ^ 8.0 8.1 8.2 8.3 8.4 8.5 Meredith, M. Brett; McMillen, C. Heather; Goodman, Jonathan T.; Hanusa, Timothy P. Ambient temperature imidazolium-based ionic liquids with tetrachloronickelate(II) anions. Polyhedron. August 2009, 28 (12): 2355–2358. doi:10.1016/j.poly.2009.04.037. 
  9. ^ Hitchcock, Peter B.; Seddon, Kenneth R.; Welton, Thomas. Hydrogen-bond acceptor abilities of tetrachlorometalate(II) complexes in ionic liquids. Journal of the Chemical Society, Dalton Transactions. 1993, (17): 2639. doi:10.1039/DT9930002639. 
  10. ^ Skaarup, Steen; Berg, Rolf Willestofte. 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. September 1978, 26 (1): 59–67. Bibcode:1978JSSCh..26...59S. doi:10.1016/0022-4596(78)90133-0.