Exploration of new organometallic complexes which enable to generate highly reactive metallic species reversibly : Foundamental chemistry and application to molecular catalysis.

分子催化在下一代高效生产化学品和材料方面的重要性得到了广泛的认可。金属有机簇合物是一种很有前途的新型分子催化材料，其合成、反应和催化等方面受到了化学家的广泛关注。我们有一个分子催化剂设计的概念，它可以适用于单核和多核金属有机催化剂：高活性金属物种是通过适当设计金属物种的辅助配体而产生的，这些金属物种在没有反应物的情况下稳定金属物种，但在与底物反应时可逆地形成活性物种。作为这种“柔性”的配体，我们已经研究了杂共轭配体，如酰胺和磺胺，以及多芳烃配体，如天青烯和榄香烯。本研究成功地合成了能够逆转…的新型有机金属配合物。此外，Bly通过配体的动态行为产生高活性物种。此外，这些新的配合物被证明对几个有机反应和聚合反应具有活性。主要研究结果如下：(1)合成了单核和双核Ru的酰胺酸盐，其中几个是配位不饱和的高活性化合物。基础化学包括结构分析、动力学行为和反应，发现了它们对烯丙基底物的化学转化和自由基类反应的催化作用。(2)新合成了磺胺钛化合物，并对其结构和溶液动力学进行了研究。结果表明，它们对烯烃聚合反应具有一定的催化活性。(3)研究了有机硅烷与π-配体的配位柔性，并将其应用于有机硅烷引发的环醚和硅氧烷的高效催化还原。(4)研究了共轭π配体配位柔性的基础化学，并分别研究了二铁化合物和钛-钼二元配合物的异双金属化学的新进展。因此，通过配体设计发现高活性的络合物实际上为这些柔性配体提供了丰富的反应化学和在分子催化中的实际应用。这些都有助于分子催化化学的进步。较少

Importance of molecular catalysis is widely recognized in efficient production of chemicals and materials in next generation. Organometallic clusters which include dual metallic species in a molecule are one of the promising candidates for new molecular catalysis, arid their synthesis, reactions, and catalysis have received much attention of chemists. We have a concept for the molecular catalyst design, which can be applicable to both mono and multinuclear organometallic catalysts : highly reactive metallic species is generated by appropriate design of auxiliary ligands of metallic species, which stabilize the metallic species in the absence of reactants, but reversibly form reactive species in reaction with substrates. As such "flexible" ligands, we have investigated heteroconjugate ligands such as amidinates and sulfonamides and polyaromatic hydrocarbon ligands such as azulenes and acenaphthylenes. The research has successfully produced new organometallic complexes, which can reversi … More bly generate highly reactive species by dynamic behavior of the ligand. Furthermore, these new complexes were proved to be active towards several organic reactions and polymerizations. The results are summarized as follows : (1)Mono and dinuclear ruthenium amidinates were synthesized, several of which were coordinatively unsaturated and highly reactive. Fundamental chemistry including structural analysis, dynamic behavior, and reactions made possible discovery of their catalysis towards chemical transformation of allylic substrates and radical-type reactions. (2)Titanium sulfonamides were newly synthesized and subjected to studies of their structure and solution dynamics. They were proved to be active towards olefin polymerization. (3)Reaction of triruthenium carbonyl clusters bound to acenaphthylenes and azulenes with orgnosilanes were investigated, and the results, i.e.coordinative flexibility of these π-ligands, were applied to highly efficient catalytic reduction of carboxylic derivatives, and silane-induced polymerization of cyclic ethers and siloxanes. (4)Fundamental chemistry on the coordinative flexibility of conjugated π-ligands and new aspects in heterobimetallic chemistry were studied on diiron compounds and Ti-M dinulcear complexes, respectively. Thus, discovery of highly reactive complexes by the ligandl design actually provides fruitful reaction chemistry of these flexible ligands and actual application to molecular catalysis. These contribute to progress of chemistry of molecular catalysis. Less