Bardak Fehmi, Atac Ahmet, Kurt Mustafa
Department of Physics, Faculty of Art & Science, Gazi University, Ankara, Turkey.
Spectrochim Acta A Mol Biomol Spectrosc. 2009 Jan;71(5):1896-900. doi: 10.1016/j.saa.2008.07.008. Epub 2008 Jul 17.
In this study the M(IN)(2)Ni(CN)(4) [where M: Co, Ni, and Cd, and IN: isonicotinic acid, abbreviated to M-Ni-IN] tetracyanonickelate and some metal halide complexes with the following stoichiometries: M(IN)(6)X(2) (M: Co; X: Cl and Br, and M: Ni; X: Cl, Br and I) and Hg(IN)X(2) (X: Cl, Br, and I) were synthesized for the first time. Certain chemical formulas were determined using elemental analysis results. The FT-IR and Raman spectra of the metal halide complexes were reported in the 4000-0 cm(-1) region. The FT-IR spectra of tetracyanonickelate complexes were also reported in the 4000-400 cm(-1) region. Vibrational assignments were given for all the observed bands. For a given series of isomorphous complexes, the sum of the difference between the values of the vibrational modes of the free isonicotinic acid and coordinated ligand was found to increase in the order of the second ionization potentials of metals. The frequency shifts were also found to be depending on the halogen. The proposed structure of tetracyanonickelate complexes consists of polymeric layers of /M-Ni(CN)(4)/(infinity) with the isonicotinic acid molecules bound directly to the metal atom.
在本研究中，首次合成了四氰基镍酸盐M(IN)(2)Ni(CN)(4) [其中M：Co、Ni和Cd，IN：异烟酸，简称为M-Ni-IN] 以及一些具有以下化学计量比的金属卤化物配合物：M(IN)(6)X(2) （M：Co；X：Cl和Br，以及M：Ni；X：Cl、Br和I）和Hg(IN)X(2) （X：Cl、Br和I）。利用元素分析结果确定了某些化学式。报道了金属卤化物配合物在4000 - 0 cm⁻¹区域的傅里叶变换红外光谱（FT-IR）和拉曼光谱。还报道了四氰基镍酸盐配合物在4000 - 400 cm⁻¹区域的FT-IR光谱。对所有观察到的谱带进行了振动归属。对于给定的一系列同构配合物，发现游离异烟酸和配位配体振动模式值之间的差值之和按金属的第二电离势顺序增加。还发现频率位移取决于卤素。所提出的四氰基镍酸盐配合物结构由/M-Ni(CN)(4)/∞的聚合物层组成，异烟酸分子直接与金属原子结合。
