Nickel(II)–PPh3 Complexes of S,N‐Substituted Thiosemicarbazones – Structure, DFT Study, and Catalytic Efficiency
Nickel(II)–PPh3 Complexes of S,N‐Substituted Thiosemicarbazones – Structure, DFT Study, and Catalytic Efficiency
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S,N 取代的缩氨基硫脲的镍 (II)-PPh3 配合物 – 结构、DFT 研究和催化效率
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发表时间：
2016
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影响因子：
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通讯作者：
B. Ülküseven
中科院分区：
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作者：
Şükriye Güveli;S. A. Cinar;O. Karahan;V. Aviyente;B. Ülküseven
合成了5种2-羟基苯乙酮缩氨基硫脲类化合物，其硫代酰胺基上分别带有[-N4 H-R-（SH）]（其中R为乙基或苯基）和[-N4 H-R-（SR 1）]（其中R/R1表示甲基/甲基、甲基/丙基或苯基/甲基）取代基。配体具有ONS或ONN供体组，并且二元配体与[Ni（PPh 3）2Cl 2]的反应产生具有通式[Ni（L）（PPh 3）]的螯合物。通过红外光谱、核磁共振氢谱和元素分析对配合物进行了表征。本文报道了两个配合物的晶体结构，一个是S-甲基-N_4-苯基取代的，另一个是S-丙基-N_4-甲基取代的氨基硫脲基配体。配合物的晶体在单斜空间群P21/n，和镍中心有一个扭曲的正方形平面环境。通过溴化苯基镁与溴苯的偶联反应考察了所制备的镍（II）配合物的催化活性，结果表明，ONN配合物比ONS配合物具有更高的产率.采用密度泛函理论（DFT）对镍配合物的催化效率进行了模拟。
Five 2-hydroxyacetophenone thiosemicarbazones with [–N4H–R–(SH)] (where R is ethyl or phenyl) and [–N4H–R–(SR1)] (where R/R1 denote methyl/methyl, methyl/propyl, or phenyl/methyl) substituents on the thioamide group were synthesized. The ligands have an ONS or ONN donor set, and the reaction of the dibasic ligands with [Ni(PPh3)2Cl2] yields chelate complexes with general formula [Ni(L)(PPh3)]. The stable solid complexes were characterized by IR and 1H NMR spectroscopy and elemental analysis. The crystallographic structures of two complexes, one with an S-methyl-N4-phenyl- and the other with an S-propyl-N4-methyl-substituted thiosemicarbazidato ligand, are reported. The complexes crystallize in the monoclinic space group P21/n, and the nickel centers have a distorted square-planar environment. The coupling reaction of phenylmagnesium bromide with bromobenzene was used to determine the catalytic activities of the nickel(II) complexes prepared, and the results show that the ONN complexes provide higher yields relative to those with ONS donors. The catalytic efficiency of the nickel complexes was modeled by using density functional theory (DFT).