Control of Electronic Envionment ofReadion Site ofTransition Metal Cluster Complexes

1.四核和五核钌多金属簇合物的合成：簇合物的反应活性很可能受原子核的影响，因为反应活性强烈地依赖于簇合物和底物之间可转移电子的数量。因此，发展一种合理的方法来合成具有更高核度和各种辅助配体的簇合物似乎是必要的，这样的簇合物在有机合成中的应用。经过四年的研究，我们发展了一系列四核和五核钌多环簇合物的合成方法，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。利用电化学方法对这些团簇的电子性质进行了估算.含钼、钨、铼和钌的双核和三核杂双金属多金属簇合物的合成：新型的含钼、钨、铼和钌的杂三金属多金属簇合物 关于我们 通过（Cp^*RuOMe）_2与双核多环配合物Cp^* Ru（μ-H）_3MH_3Cp^*（M = Mo，W）反应，合成了钌和第六族金属（Cp ^* Ru）_2（Cp^*M）（μ-H）_5（M = Mo，W）和（Cp^*Ru）（Cp^*W）_2H_7。还合成了含钌和钌的多金属配合物Cp^*Ru（μ-H）_3ReH_2Cp^* 和（Cp^*Ru）_2（Cp^*Re）（μ-H）_7.三钌簇合物诱导肼的N-N键断裂：[（Cp^*Ru）_3H_6]+与肼反应导致N-N键断裂生成（Cp^*Ru）_3（μ-NH）H_3。该化合物进一步与肼反应生成（Cp*Ru）_3（μ-NH）_2H。这些μ_3-亚氨基配合物在氢化反应中生成（Cp^*Ru）_3H_5，同时释放出氨.三钌多配位原子簇诱导氨的N-H键断裂：钌多配位原子簇（Cp^*Ru）_3H_5与氨反应生成单μ_3亚氨基配合物和二氢，这是两个N-H键活化的结果。在反应中，（Cp^*Ru）_3（μ-O）（μ-H）_3促进了N-H键的断裂。少

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