镍（II）和锌（II）的二茂铁螯合异蝎形配合物的合成与表征
Synthesis and characterization of ferrocene-chelating heteroscorpionate complexes of nickel(II) and zinc(II).
作者信息
Abubekerov Mark, Diaconescu Paula L
机构信息
Department of Chemistry and Biochemistry, University of California , Los Angeles, California 90095, United States.
出版信息
Inorg Chem. 2015 Feb 16;54(4):1778-84. doi: 10.1021/ic502691b. Epub 2015 Jan 21.
The first example of a ferrocene-chelating heteroscorpionate, [Li(THF)2][fc(PPh2)(BH[(3,5-Me)2pz]2)] ((fc(P,B))Li(THF)2, fc = 1,1'-ferrocenediyl) is described. Starting from a previously reported compound, fcBr(PPh2), a series of ferrocene derivatives, fc(PPh2)(B[OMe]2), [Li(OEt2)][fc(PPh2)(BH3)], [Li(THF)2][fc(PPh2)(BH[(3,5-Me)2pz]2)] (pz = pyrazole), was isolated and characterized. Compound (fc(P,B))Li(THF)2 allowed the synthesis of the corresponding nickel and zinc complexes, (fc(P,B))NiCl, (fc(P,B))NiMe, (fc(P,B))ZnCl, and (fc(P,B))ZnMe. All compounds were characterized by NMR spectroscopy, while the zinc and nickel complexes were also characterized by X-ray crystallography. The redox behavior of (fc(P,B))NiCl, (fc(P,B))NiMe, (fc(P,B))ZnCl, and (fc(P,B))ZnMe was studied by cyclic voltammetry and supported by density functional theory calculations.
报道了首例二茂铁螯合杂环配体化合物[Li(THF)₂][fc(PPh₂)(BH[(3,5-Me)₂pz]₂)] ((fc(P,B))Li(THF)₂, fc = 1,1'-二茂铁二基)。从先前报道的化合物fcBr(PPh₂)出发，分离并表征了一系列二茂铁衍生物，fc(PPh₂)(B[OMe]₂)、[Li(OEt₂)][fc(PPh₂)(BH₃)]、[Li(THF)₂][fc(PPh₂)(BH[(3,5-Me)₂pz]₂)] (pz = 吡唑)。化合物(fc(P,B))Li(THF)₂可用于合成相应的镍和锌配合物，(fc(P,B))NiCl、(fc(P,B))NiMe、(fc(P,B))ZnCl和(fc(P,B))ZnMe。所有化合物均通过核磁共振光谱进行表征，而锌和镍配合物还通过X射线晶体学进行表征。通过循环伏安法研究了(fc(P,B))NiCl、(fc(P,B))NiMe、(fc(P,B))ZnCl和(fc(P,B))ZnMe的氧化还原行为，并得到密度泛函理论计算的支持。
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