Stereochemistry, Photochemistry, and Magnetism of Sulfur-Bridged Metal-Cluster Complexes

本研究主要关注硫桥接的三核或四核钼钨团簇配合物的通用性，不仅关注与取代和氧化还原反应有关的金属，还关注桥接硫的反应性。通过硫桥不完全立方型簇与乙炔反应，得到了具有硫碳键的簇配合物，并对其进行了表征，测定了其x射线结构。此外，还明确了硫/氧桥接钨簇的桥接硫的反应性受到配体的影响。硫碳键形成的发现促使我们发现了新的钼、钨和铬化合物，其中一些表现出光致变色。金属掺入反应是我们多年来研究的主题之一，也得到了发展：合成了新的钼镓、钼锑和钼镉团簇并对其进行了表征。合成了一种硫桥接的立方型硝基三乙酸钨镍簇，并对其进行了分离和表征。从硫氧桥接的不完全立方型簇中得到去质子化乙二胺簇。此外，还分离出了硫桥不完全立方型亚氨基二乙酰钼簇的4个异构体，用x射线晶体学测定了其中3个异构体的结构，并检测了4个异构体之间的异构化。

This research has pursued mainly the versatile nature of sulfur-bridged tri- or tetra-nuclear molybdenum and tungsten cluster complexes, and has paid attention not only to metal concerning substitution and redox reaction, but also to the reactivity of bridging sulfur.Through the reaction of sulfur-bridged incomplete cubane-type cluster with acetylene, cluster complexes having sulfur-carbon bonds were obtained and characterized, and their X-ray structures were determined. In addition it was made clear that the reactivity of bridging sulfurs of sulfur/oxygen-bridged tungsten clusters is influenced by ligands. The finding of the sulfur-carbon bond formation induced us to find novel molybdenum, tungsten, and chromium compounds, some of which show photochromism.Metal incorporation reaction, which is one of our research theme for years, has also been developed : novel molybdenum gallium, molybdenum-antimony, and molybdenum-cadmium clusters have been synthesized and characterized.A sulfur-bridged cubane-type nitrilotriacetato tungsten-nickel cluster has been synthesized, from which a hydrazine coordinated complex was isolated and characterized.Deprotonated ethylenediamine clusters were obtained from sulfur/oxygen bridged incomplete cubane-type clusters. In addition, four isomers of sulfur-bridged incomplete cubane-type iminodiacetato molybdenum clusters have been isolated, three structures of them were determined by X-ray crystallography, and isomerization among the four isomers was detected.