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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的认可。分子中含有双金属物种的有机簇合物是一种很有希望的新型分子催化剂，其合成、反应和催化作用受到了化学家们的广泛关注。我们有一个概念的分子催化剂的设计，它可以适用于单核和多核有机金属催化剂：高活性的金属物种是由金属物种的辅助配体的适当的设计，稳定的金属物种在没有反应物，但可逆地形成反应物种与基板反应生成。作为这样的“柔性”配体，我们已经研究了杂共轭配体如脒基和磺酰胺以及多环芳烃配体如甘菊环和苊环。这项研究已经成功地产生了新的有机金属配合物，它可以逆转， ...更多信息通过配体的动力学行为可产生高活性物质。此外，这些新的配合物被证明是积极的对几个有机反应和聚合。主要研究结果如下：（1）合成了单核和双核脒基钌配合物，其中有几种是配位不饱和的，反应活性很高。包括结构分析、动力学行为和反应的基础化学使发现它们对烯丙基底物的化学转化和自由基型反应的催化成为可能。（2）合成了新型的钛磺酰胺类化合物，并对其结构和溶液动力学进行了研究。它们被证明对烯烃聚合具有活性。（3）研究了苊烯和奥基上的三钌羰基簇合物与有机硅烷的反应，并将这些π-配体的配位灵活性应用于羧酸衍生物的高效催化还原，以及环醚和硅氧烷的硅烷引发聚合。（4）研究了共轭π配体配位灵活性的基础化学和二铁化合物和钛-钼二硫配合物的杂环化学新方向。因此，通过配体1设计发现高反应性络合物实际上提供了这些柔性配体的富有成效的反应化学和分子催化的实际应用。这些都有助于分子催化化学的发展。少