镍氰酸盐

镍氰酸盐是一类氰配位的镍化合物。最重要的镍氰酸盐是四氰合镍(II)酸盐，它包含着[Ni(CN)₄]²⁻阴离子。它可以存在于溶液中或固体中。该配离子具有围绕中心镍离子排列成正方形的氰根。离子的对称性为D_4h。从镍原子到碳的距离为1.87Å，碳-氮距离为1.16Å。^[1]四氰合镍酸根可以在溶液中被电化学氧化为四氰合镍(III)酸根[Ni(CN)₄]⁻。[Ni(CN)₄]⁻不稳定，其中的Ni(III)可以将CN^-氧化为OCN⁻。^[2][Ni(CN)₄]⁻可以进一步配位2个氰基，形成[Ni(CN)₆]^3-。^[2]

与烷基二胺和其他金属离子结合，四氰合镍酸根离子可以形成可以容纳有机分子的笼结构，它是一种Hofmann-diam型包合物。^[3]

如果遇到强还原性试剂，如Yb²⁺，[Ni(CN)₄]²⁻可以被还原为[Ni₂(CN)₆]²⁻，其中镍为+1价。

参考文献

^ Loewenschuss, A.; Marcus, Y. Standard Thermodynamic Functions of Some Isolated Ions at 100-1000 К (PDF). J. Phys. Chem. Ref. Data. 1996, 25 (6): 1502 [30 April 2016]. （原始内容 (PDF)存档于2012-10-10）.
^ ^2.0 ^2.1 Wang, Yi Lai; Beach, Mark W.; Pappenhagen, Thomas L.; Margerum, Dale W. Mixed-ligand complexes of tetracyanonickelate(III) and dynamic Jahn-Teller distortions of hexacyanonickelate(III). Inorganic Chemistry. November 1988, 27 (24): 4464–4472. doi:10.1021/ic00297a025.
^ Şenyel, Mustafa; Raci Sertbakan, T.; Kürkçüoğ, Güneş; Kasap, Ergün; Kantarci, Ziya. An Infrared Spectroscopic Study on the Hofmann-diam-type 1,12-Diaminododecanemetal(II) Tetracyanonickelate(II)-aromatic Guest Clathrates: M(H2N(CH2)12NH2)Ni(CN)4ċG(M=Co, Ni or Cd; G = Benzene, Naphthalene, Anthracene, Phenanthrene or Biphenyl). Journal of Inclusion Phenomena and Macrocyclic Chemistry. 2001, 39 (1/2): 175–180. doi:10.1023/A:1008141726024.

[1] Loewenschuss, A.; Marcus, Y. Standard Thermodynamic Functions of Some Isolated Ions at 100-1000 К (PDF). J. Phys. Chem. Ref. Data. 1996, 25 (6): 1502 [30 April 2016]. （原始内容 (PDF)存档于2012-10-10）.

[wangyi-2] 2.0 ^2.1 Wang, Yi Lai; Beach, Mark W.; Pappenhagen, Thomas L.; Margerum, Dale W. Mixed-ligand complexes of tetracyanonickelate(III) and dynamic Jahn-Teller distortions of hexacyanonickelate(III). Inorganic Chemistry. November 1988, 27 (24): 4464–4472. doi:10.1021/ic00297a025.

[3] Şenyel, Mustafa; Raci Sertbakan, T.; Kürkçüoğ, Güneş; Kasap, Ergün; Kantarci, Ziya. An Infrared Spectroscopic Study on the Hofmann-diam-type 1,12-Diaminododecanemetal(II) Tetracyanonickelate(II)-aromatic Guest Clathrates: M(H2N(CH2)12NH2)Ni(CN)4ċG(M=Co, Ni or Cd; G = Benzene, Naphthalene, Anthracene, Phenanthrene or Biphenyl). Journal of Inclusion Phenomena and Macrocyclic Chemistry. 2001, 39 (1/2): 175–180. doi:10.1023/A:1008141726024.

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