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Control of Electronic Envionment ofReadion Site ofTransition Metal Cluster Complexes

过渡金属簇配合物读取位点电子环境的控制

基本信息

批准号：
14078210
负责人：
SUZUKI Hiroharu
金额：
$ 19.84万
依托单位：
Tokyo Institute of Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research on Priority Areas
财政年份：
2002
资助国家：
日本
起止时间：
2002 至 2005
项目状态：
已结题

项目摘要

1. Synthesis of Tetra-and Pentanuclear Ruthenium Polyhydrido Clusters : The reactivity of cluster complex is most probably affected by the nuclearity because the reactivity strongly depends on the number of transferable electrons between the cluster and substrate. Thus the development of a rational method for the synthesis of clusters with higher nuclearity and a variety of auxiliary ligands seems to be essential for the application of such cluster to organic synthesis. After a four-year term of the research, we developed synthetic methods of a variety of tetra-and pentanuclear ruthenium polyhydrido clusters, such as (CpRu)_4H_6, (CpRu)_3(Cp^*Ru)H_6, (CpRu)_2(Cp^*Ru)_2H_6, (CpRu)(Cp^*Ru)_3H_6, and (CpRu)_5H_7. Electronic properties of these clusters were estimated by means of electrochemical technique.2. Synthesis of Di-and Trinuclear Heterobimatallic Polyhydrido Clusters Containing Molybdenum, Tungsten, Rhenium, and Ruthenium : Novel heterotrimetallic polyhydrido complexes containing … More ruthenium and group 6 metals,(Cp^*Ru)_2(Cp^*M)(μ-H)_5 (M = Mo, W) and (Cp^*Ru)(Cp^*W)_2H_7, were synthesize by the reaction of (Cp^*RuOMe)_2 with dinuclear polyhydrido complexes Cp^*Ru(μ-H)_3MH_3Cp^* (M = Mo, W). Polyhydrido complexes containing both ruthenium and rhenium, Cp^*Ru(μ-H)_3ReH_2Cp^* and (Cp^*Ru)_2(Cp^*Re)(μ-H)_7, were also synthesized.3. Cleavage of the N-N Bond of Hydrazine Induced by Triruthenium Cluster : The reaction of [(Cp^*Ru)_3H_6]+ with hydrazine led to the the formation of (Cp^*Ru)_3(μ-NH)H_3 as a result of cleavage of the N-N bond. This compound further reacted with hydrazine to yield (Cp*Ru)_3(μ-NH)_2H. These μ_3-imido complexes underwent hydrogenation to generate (Cp^*Ru)_3H_5 together with liberation of ammonia.4. Cleavage of N-H Bonds of Ammonia Induced by Triruthenium Polyhydrido Clusters : Ruthenium polyhydrido cluster (Cp^*Ru)_3H_5 reacted with ammonia to produce a mono-μ_3imido complex and dihydrogen as a result of activation of the two N-H bonds. The N-H bond cleavage was accelerated in the reaction with a proxo complex, (Cp^*Ru)_3(μ-O)(μ-H)_3. Less

1.四核和五核Ru多氢簇合物的合成：簇合物的反应性很可能受到成核性的影响，因为反应性强烈地依赖于团簇和底物之间的可转移电子的数量。因此，发展一种合理的方法来合成具有较高核度的簇合物和各种辅助配体似乎是将这种簇合物应用于有机合成的关键。经过四年的研究，我们发展了各种四核和五核Ru多氢簇合物的合成方法，如(CpRu)_4H_6，(CpRu)_3(Cp^*Ru)H_6，(CpRu)_2(Cp^*Ru)_2H_6，(CpRu)(Cp^*Ru)_3H_6和(CpRu)_5H_7，并用电化学技术对这些簇合物的电子性质进行了估算。含钼、钨、Re、Ru的二核和三核杂双金属多氢簇合物的合成：含…的新型杂三金属多氢配合物通过(Cp^*Ru)_2与双核多氢配合物Cp^*Ru(μ-H)_3Mp^*(M=Mo，W)反应，合成了更多的Ru和6族金属(Cp^*Ru)_2(Cp^*M)(μ-H)_5(M=Mo，W)和(Cp^*Ru)(Cp^*W)_2H_7。合成了同时含有Ru和Re的多元配合物Cp^*Ru(μ-H)_3ReH_2Cp^*和(Cp^*Ru)_2(Cp^*Re)(μ-H)_7。三Ru簇合肼的N-N键断裂：[(Cp^*Ru)_3H_6]+与肼反应生成(Cp^*Ru)_3(μ-NH)H_3。该化合物与肼反应生成(Cp*Ru)_3(μ-NH)_2H。这些μ_3-亚胺络合物在氢化生成(Cp^*Ru)_3H_5的同时还释放了氨气。Ru多氢簇合物(Cp^*Ru)_3H5与氨反应生成单μ_3imido络合物和二氢化合物，两个N-H键被激活。与邻位络合物(Cp^*Ru)_3(μ-O)(μ-H)_3的反应加速了N-H键的断裂。