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。四核和戊核氟苯二元组的合成：聚类络合物的反应性很可能受核性的影响，因为反应性强烈取决于簇和底物之间转移的电子的数量。开发一种合成具有较高核性和各种辅助配体的簇的合理方法似乎对于将这种簇应用于有机合成至关重要。经过四年的研究，我们开发了多种四核和戊型五氢氢化氢酶簇的合成方法，例如（cpru）_4H_6，（cpru）_3（cp^*ru）H_6，H_6，（cpru）（CPRU）_5H_7。通过电化学技术估算这些簇的电子性能2。含有钼，钨，rhenium和ruthenium的Di-and di-di-di-di-di-di-brotimaticallicallicallicallic多氢化簇簇的合成：新型的杂质金属多氢氢化氢菌络合物，含有…更多的ruthenium和6个金属和（cp^*ru）_2（cp^*ru）_2（cp^*m）（cp^*m）（w we），（cp^*ru）（cp^*w）_2H_7，是通过（cp^*ruome）_2与稀释的多氢氢核络合物Cp^*ru（μ-h）_3MH_3CP^*（m = mo，w）合成的。还合成了含有氟苯和ruthenium，cp^*ru（μ-h）_3Reh_2cp^*和（cp^*ru）_2（cp^*re）（μ-h）_7的多氢化物复合物。三位苯簇诱导的肼的N-N键的切割：[（cp^*ru）_3H_6]+与氢嗪的反应导致形成（Cp^*ru）_3（μ-NH）H_3是N-N键的裂解的结果。该化合物进一步与肼反应（CP*RU）_3（μ-NH）_2H。这些μ_3-iMido复合物经过了氢化，以产生（cp^*ru）_3H_5以及氨的解放4。由三位苯二氢簇诱导的氨的N-H键的切割：ruthenium多氢hdro簇（CP^*RU）_3H_5与氨反应产生单nimido复合物和二氢，这是两种N-H-H键的激活。 N-H键裂解在与Proxo复合物（CP^*RU）_3（μ-O）（μ-H）_3的反应中加速了。较少的