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

硫桥金属簇配合物的立体化学、光化学和磁性

• 批准号: 08454215
• 负责人: SHIBAHARA Takashi
• 金额: $ 5.06万
• 依托单位: Okayama University of Science
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1996
• 资助国家: 日本
• 起止时间: 1996 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08454215/
• 关键词: molybdenum; tungsten; sulfur-bridge; metalcluster; complex; photochromism; photochemistry; sterochemistry; カドミウム; ニッケル; アセチレン; イミノ二酢酸; 異性化; クラスター; 光学活性; ガリウム; 磁性; 分子軌道計算

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.

本研究主要是探索硫桥连的三核或四核钼、钨簇合物的多功能性，不仅关注与金属有关的取代和氧化还原反应，而且关注硫桥连的反应活性，通过硫桥连的不完全立方烷型簇合物与乙炔的反应，得到并表征了具有硫-碳键的簇合物，测定了它们的X射线结构。此外，还发现硫氧桥联钨簇合物中桥硫的反应活性受配体的影响。硫-碳键形成的发现促使我们发现了新的钼、钨和铬化合物，其中一些化合物显示出光致变色性。金属掺入反应也是我们多年来的研究主题之一：新的钼镓，铼-锑，合成了一种硫桥联立方烷型次氮基三乙酰基钨-镉簇合物，合成了镍簇合物，并从其上分离出一个肼配位化合物，从硫氧桥联的不完全立方烷型簇合物上得到了去质子化的乙二胺簇合物。此外，还分离出了硫桥不完全立方烷型亚氨基二乙酰基钼簇合物的四种异构体，用X射线晶体学方法确定了它们的三种结构，并发现了四种异构体之间的异构化现象。

项目成果

G.Sakane, K.Hashimoto, M.Takahashi, M.Takeda, and T.Shibahara: "Sulfur-Bridged Sandwich Cubane-Type Molybdenum-Antimony Cluster. Synthesis, X-ray Structure, and ^<121>Sb MOssbauer Spectra of [(H_2O)_9Mo_3S_4SbS_4Mo_3(H_2O)_9](CH_3C_6H_4SO_3)_8・24H_2O" Ino

G.Sakane、K.Hashimoto、M.Takahashi、M.Takeda 和 T.Shibahara：“硫桥三明治古巴烷型钼锑簇。合成、X 射线结构和 ^<121>Sb MOssbauer 光谱[(H_2O)_9Mo_3S_4SbS_4Mo_3(H_2O)_9](CH_3C_6H_4SO_3)_8・24H_2O" 井野

T. Shibahara et al.: "Sulfur-Bridged Cubane-Type Holybdenm-Gallium Clusters with Mo_3Go_1S_4^<n+>‥‥" Inorg, Chem,. 36. 1702-1706 (1997)

T. Shibahara 等人：“含 Mo_3Go_1S_4^<n+>‥‥ 的硫桥古巴烷型 Holybdenm-镓簇” Inorg, Chem, 36. 1702-1706 (1997)

H.Akashi,N.Uryu and T.Shibahara: "Magnetic susceptibility analysis of mixed metal cubane-type cluster Oomplexes,[tetra-・・・・" Inorg,chem,Acta,. 261. 53-57 (1997)

H.Akashi、N.Uryu 和 T.Shibahara：“混合金属立方烷型团簇 Oomplexes 的磁化率分析，[tetra-...”Inorg,chem,Acta,。

柴原隆志他4名: "Sulfur-Bridged Cubane-Type Molybdenum-Gallium Clusters" Inorganic Chemistry. (4月発行予定). (1997)

Takashi Shibahara 等 4 人：“Sulfur-Bridged Cubane-Type Molybdenum-Gallium Clusters”Inorganic Chemistry（计划于 4 月出版）。

R. Miyamoto, S. Kawata, M. Iwazumi, H. Akashi, and T. Shibahara: "EPR Studies of the Mixed-Metal Cubane-Type Complex Having a [Mo_3CuS_4(H_2O)_<10>]^<4+>Core" Inorg. Chem,. 36. 542-546 (1997)

R. Miyamoto、S. Kawata、M. Iwazumi、H. Akashi 和 T. Shibahara：“具有 [Mo_3CuS_4(H_2O)_<10>]^<4 > 核的混合金属古巴烷型配合物的 EPR 研究