金属の結合様式に基づく硫黄架橋多核錯体の組織化と制御

我们研究了多核配合物选择性形成的可能性，这些多核配合物是由单核配合物与不同的金属离子反应而成的，取决于配位方式。在本工作中，首先选择了铬(III)离子或单核配合物，因为它们带有未成对的电子，对硫给体原子的稳定性差，反应活性高。八面体铬(III)络合物在金属离子周围的选择性聚集与未成对的电子和金属中心之间的相互作用有关。八面体配合物与金属离子以直线型配位方式反应，得到立体选择性的五核配合物。金属离子的反应既可以是线性配位，也可以是四面体配位，分别得到五核和八核配合物。此外，顺式络合物与钯(II)离子反应，得到双核、三核或六核配合物，它们是由氯离子控制结构的方形平面配合物和三角双衍生物。当配体不太容易被其他配体取代的方形平面配合物与方形平面配合物反应时，选择性地形成双核配合物而不是六核配合物。最后，通过对八面体单核配合物进行适当的氧化条件处理，选择性地形成了比较稳定的具有二硫键的双核配合物。对所有立体选择性合成的多核配合物的立体化学、光谱化学、电化学和磁性进行了研究。

We have investigated the possibility of the selective formation for the polynuclear complexes, which are given by the reactions of the mononuclear complexes with various metal ions depending on the coordination modes. In this work, firstly, the chromium (III) ions or mononuclear complexes have been selected, since they take unpaired electrons, and poor stability and highly reactivity for the sulfur donor atoms. The selective aggregations of the octahedral chromium (III) complexes around the metal ions are performed and discussed in relation to the unpaired electrons and the interactions between the metal centers. The reactions of the octahedral complexes with the metal ions being the linear-type coordination modes gave stereoselectively the pentanuclear complexes. The reactions of the metal ions being possible for both of the linear-and tetrahedral-type coordination modes can give the pentanuclear and octanuclear complexes, respectively. Further, the cis complexes react with the palladium (II) ion to give the dinuclear complexes and trinuclear or hexanuclear complexes being square-planar complexes and trigonal-bipy-ramidal, whose structures are controlled by the chloride ions. When the square-planar complexes, in which the ligands are less susceptible to substirution of other ligands, reacts with the square-planar complexes, the dinuclear complexes are selectively formed without the hexanuclear complexes. Finally, the fairly stable dinuclear complexes with the disulfide bond are selectively formed by treating with suitable oxidation conditions for the octahedral mononuclear complexes. All of the stereoselectively obtained polynuclear complexes are studied in regard to the sterochemical, spectrochemical, electrochemical, and magnetic properties.