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的选择性形成的可能性，这是由单核配合物与各种金属离子的反应取决于配位模式。在这项工作中，首先，铬（III）离子或单核配合物已被选择，因为它们采取不成对的电子，和差的稳定性和高反应性的硫供体原子。的八面体铬（III）配合物周围的金属离子的选择性聚集进行和讨论有关的未成对电子和金属中心之间的相互作用。八面体配合物与金属离子的配位反应为线型配位，立体选择性地得到五核配合物。金属离子的配位反应既可以是线型配位，也可以是四面体配位，因此可以分别得到五核和八核配合物。此外，顺式配合物与钯（II）离子反应，得到双核配合物和三核或六核配合物，它们是正方形平面配合物和三角形联吡酰胺，其结构由氯离子控制。当其中配体不易被其它配体取代的正方形平面配合物与正方形平面配合物反应时，选择性地形成双核配合物而没有六核配合物。最后，通过对八面体单核配合物进行适当的氧化处理，选择性地形成了具有二硫键的相当稳定的双核配合物。所有的立体选择性获得的多核配合物的立体化学，光谱化学，电化学和磁性方面进行了研究。

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.