四氯鎳酸根

四氯鎳酸根離子是一種金屬配合物,化學式為[NiCl4]2−,其鹽稱作四氯鎳酸鹽。四氯鎳酸根離子可以與各種各樣的陽離子鍵合,但常見的包括四乙基銨陽離子[1]

四面體四氯鎳酸絡離子
(Et4N)2NiCl4樣品。

當濃氯化鋰和氯化鎳的水溶液混合在一起時,它們只會形成五水氯絡合物:[Ni(H2O)5Cl]+。然而,在其他有機溶劑或熔融的鹽中,它們可以形成四氯鎳酸根離子。如果將鎳配分到胺的環己烷溶液中,鎳就可以從這些鹽的水或甲醇溶液中被分離出來。[2]

(R3NH)2[NiCl4]之類的有機銨鹽通常可以發生熱致變色(R = Me, Et, Pr)。在近室溫的環境下,這些鹽呈黃色,但它們在70 °C下會變成藍色。亮藍色是四面體的[NiCl4]2−的特徵,而強度是拉波特規則導致的。鹽呈黃色是因為它們生成了由八面體Ni中心組成的聚合物。相應的四溴鎳酸鹽在較低的溫度下也會發生熱致變色的。[3]

歷史

1944年,Remy和Meyer將氯化銫和三氯化銫鎳一起熔化時,首次觀察到由四氯鎳酸根離子引起的藍色。[4]

化合物

公式 名稱 結構 備註 參考
Cs2NiCl4 四氯鎳酸銫 只在超過70 °C的環境下保持藍色 [4]
[(CH3)4N]2NiCl4 四甲基四氯鎳酸銨 深藍色 [5]
[(C2H5)4N]2NiCl4 四乙基四氯鎳酸銨英語Tetraethylammonium tetrachloronickelate [6] [4]
[H2NN(CH3)3]2NiCl4 1,1,1-三甲基肼正離子四氯鎳鹽(1,1,1-三甲基四氯鎳酸𨥙) 只在超過145 °C的環境下保持藍色,在此溫度以下呈黃色 [7]
[(C6H5)4As]2NiCl4 雙四苯基砷正離子(鎓)四氯鎳酸鹽 藍色,熔點199.5 °C [5]
[(C6H5)3CH3As]2NiCl4 雙三苯甲基砷正離子(鎓)四氯鎳酸鹽 藍色 [4]
[C2mim]2NiCl4 1-乙基-3-甲基咪唑正離子(鎓)四氯鎳(II)酸鹽 四方晶系,I41/a
a=14.112,c=19.436,V=3871.1,Z=8,密度=1.47,MW=422.84
熔點92 °C [8] [9]
[C4mim]2NiCl4 1-丁基-3-甲基咪唑正離子(鎓)四氯鎳(II)酸鹽 深藍色,熔點56 °C [8]
[C5mim]2NiCl4 1-戊基-3-甲基咪唑正離子(鎓)四氯鎳(II)酸鹽 深藍色液體 [8]
[C6mim]2NiCl4 1-己基-3-甲基咪唑正離子(鎓)四氯鎳(II)酸鹽 深藍色液體 [8]
[C7mim]2NiCl4 1-庚基-3-甲基咪唑正離子(鎓)四氯鎳(II)酸鹽 深藍色液體 [8]
[C8mim]2NiCl4 1-辛基-3-甲基咪唑正離子(鎓)四氯鎳(II)酸鹽 深藍色液體 [8]
[NH3CH2CH2NH3]NiCl4 乙二胺正離子四氯鎳(II)酸鹽 鈣鈦礦層狀,空間群P21/c
a=8.441,b=6.995,c=6.943,β=92.925,Z=2
棕色,與Mn、Cu、Pd和Cd化合物同構 [10]

有關物質

參考文獻

  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.