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

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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.