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

探索能够可逆地产生高活性金属物质的新型有机金属配合物：基础化学及其在分子催化中的应用。

基本信息

批准号：
13450374
负责人：
NAGASHIMA Hideo
金额：
$ 8.26万
依托单位：
Kyushu University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2001
资助国家：
日本
起止时间：
2001 至 2003
项目状态：
已结题

项目摘要

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

分子催化在下一代化学品和材料的高效生产中的重要性得到了广泛认可，分子中包含双金属物质的有机金属簇是新型分子催化的有希望的候选者之一，其合成、反应和催化已受到广泛关注。我们有一个分子催化剂设计概念，可适用于单核和多核有机金属催化剂：通过适当设计金属物质的辅助配体产生高反应性金属物质，它在没有反应物的情况下稳定金属物质，但在与底物反应时可逆地形成反应性物质，作为这种“柔性”配体，我们研究了脒盐和磺酰胺等杂合物配体以及甘菊环和苊等多芳烃配体。已成功生产出新的有机金属配合物，它可以通过配体的动态行为逆转产生高反应性物种此外，这些新配合物已被证明。结果总结如下：（1）合成了单核和双核钌脒盐，其中一些是配位不饱和的和高反应性的基础化学，包括结构分析、动力学行为和反应。 (2)新合成了钛磺酰胺化合物并对其结构和溶液动力学进行了研究。 (3)研究了与苊和甘菊环结合的三钌羰基簇与有机硅烷的反应，并将这些π配体的配位灵活性应用于羧基的高效催化还原。 (4)基础化学分别在二铁化合物和 Ti-M 双核配合物上研究了共轭 π 配体的配位灵活性和异双金属化学的新方面。这些对分子催化化学的进步贡献较少。