Control of Electronic Envionment ofReadion Site ofTransition Metal Cluster Complexes

1. 四核和五核钌多羟基团簇的合成：团簇配合物的反应性很可能受核的影响，因为反应性很大程度上取决于团簇和底物之间可转移电子的数量。因此，开发一种合理的方法来合成具有高核的团簇和各种辅助配体似乎是将这种团簇应用于有机合成的必要条件。经过4年的研究，我们开发了多种四核和五核钌多羟基团簇的合成方法，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。利用电化学技术对这些团簇的电子性质进行了估计。用（Cp^*RuOMe）_2与双核多羟基配合物Cp^*Ru(μ-H)_3MH_3Cp^* （M = Mo， W）反应，合成了新型含钌和6族金属的杂三金属多羟基配合物（Cp^*Ru）_2(Cp^*M)(μ-H)_5 （M = Mo， W）和（Cp^*Ru）（Cp^*W）_2H_7。同时合成了含有钌和铼的多羟基配合物Cp^*Ru(μ-H)_3ReH_2Cp^*和（Cp^*Ru）_2(Cp^*Re)(μ-H)_7。三钌团簇诱导肼的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-亚胺配合物经过氢化反应生成（Cp^*Ru）_3H_5，并伴有氨的释放。三钌多羟基团簇诱导氨的N-H键断裂：钌多羟基团簇（Cp^*Ru）_3H_5与氨反应，两个N-H键被激活，生成单μ _3亚胺配合物和二氢。催化络合物（Cp^*Ru）_3(μ-O)(μ-H)_3加速了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