Synthesis and X-ray Crystal Structure of the First Mononuclear Nickel(II) Alkane Thiolate Complex with a Mixed (S,N,N,O) Ligand Field†
Synthesis and X-ray Crystal Structure of the First Mononuclear Nickel(II) Alkane Thiolate Complex with a Mixed (S,N,N,O) Ligand Field†
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第一个具有混合 (S,N,N,O) 配体场的单核硫醇镍 (II) 络合物的合成和 X 射线晶体结构†
DOI：
10.1002/cber.19961291007
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发表时间：
1996
期刊：
影响因子：
--
通讯作者：
L. Seidel
中科院分区：
文献类型：
--
作者：
A. Berkessel;M. Bolte;T. Neumann;L. Seidel
描述了一个带有巯基甲基作为额外结合位点的手性五齿二氢salen配体的六步合成。当此配体与镍（II）盐处理，得到一个平面的四配位的镍螯合物，而不是预期的五配位物种。该复合物进行了充分的表征，包括X射线晶体学。晶体结构表明，镍离子是由硫醇阴离子，胺和亚胺的配体的氮原子，并通过一个酚阴离子配位。配体的第二个酚氧原子不参与镍离子的配位。该螯合物是第一个具有混合（S，N，N，O）配体场的单核镍（II）硫醇盐络合物。循环伏安法未显示高达-2.1V（相对于Fc/Fc+）的还原。在阳极范围内，没有可逆的，但两个不可逆的氧化过程进行了观察。
The six-step synthesis of a chiral, pentadentate dihydrosalen ligand, carrying a mercaptomethyl group as additional binding site, is described. When this ligand was treated with nickel(II) salts, a planar tetracoordinated nickel chelate was obtained, and not the expected pentacoordinated species. This complex was fully characterized, including X-ray crystallography. The crystal structure revealed that the nickel ion is coordinated by the thiolate anion, both the amine and the imine nitrogen atoms of the ligand, and by one phenolate anion. The second phenolic oxygen atom of the ligand does not participate in the coordination of the nickel ion. This chelate is the first mononuclear nickel(II) thiolate complex having a mixed (S,N,N,O) ligand field. Cyclic voltammetry did not indicate a reduction up to –2.1 V (vs. Fc/Fc+). In the anodic range, no reversible but two irreversible oxidation processes were observed.