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Development of Novel Transformation Reactions of Silicon Compounds Utilizing Specific Reactivity of Transition Metal-Silylene Complexes

利用过渡金属-硅烯配合物的特异反应性开发硅化合物的新型转化反应

基本信息

批准号：
14204065
负责人：
TOBITA Hiromi
金额：
$ 36.19万
依托单位：
Tohoku University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (A)
财政年份：
2002
资助国家：
日本
起止时间：
2002 至 2004
项目状态：
已结题

项目摘要

Through the mechanistic studies using silyl(silylene) complexes stabilized by bulky mesityl groups, we proved that the 1,3-migration of a substituent from the silyl ligand to the silylene ligand and the 1,2-migration of the silyl ligand from the metal to the silylene ligand proceed reversibly under mild conditions. We also found that an aryl ligand migrates reversibly between a metal center and a silylene ligand in some tungsten complexes. With the help of steric protection of a bulky alkyl group, we synthesized and stabilized a silylenetungsten complex having a hydrogen on the silylene ligand, and succeeded in determining the crystal structure for the first time for this type of complex. This crystal structure analysis revealed that a hydride ligand bridges over the tungsten-silicon double bond. This hydrosilylene complex was found to react with various polar organic molecules such as nitriles, ketones, enones, and methanol to give the products formed through hydrosilylation, [4+2] cy … More cloaddition, etc. By these researches, we demonstrated that, on several silylene complexes, the metal-silicon double bond plays an important role to induce specific interactions and rearrangements, and causes new types of chemical conversions on silicon compounds.Three-membered metallacycles composed of silicon, phosphorus, and iron were first synthesized, and the structure, rearrangement reaction, dimerization reaction, and reactions with various polar molecules were investigated. These reactions all proceeded accompanied by the cleavage of the silicon-phosphorus bond, probably because, in these metallacycles, contribution of the canonical form of phosphide(silylene) complex is substantial and causes strong polarization of the silicon-phosphorus bond, and also the ring strain activates the bond. An analogous formation and reactions of metallacycles were also observed in the systems containing sulfur or tellurium instead of phosphorus, whereas in the system containing nitrogen, an interesting reaction involving migration of the aminosilyl ligand onto a negative atom was found to occur. Less

通过使用大基团稳定的甲硅烷基(亚硅基)配合物的机理研究，我们证明了取代基从甲硅烷基配体到亚硅基配体的1,3-迁移和甲硅烷基配体从金属到亚硅基配体的1,2-迁移在温和条件下可逆进行。我们还发现，在一些钨配合物中，芳基配体在金属中心和亚硅基配体之间可逆迁移。借助大烷基的空间保护，我们合成并稳定了硅基配体上具有氢的硅基钨配合物，并首次成功确定了此类配合物的晶体结构。该晶体结构分析表明，氢化物配体桥接在钨-硅双键上。这种氢化硅烯配合物被发现可以与各种极性有机分子（如腈、酮、烯酮和甲醇）反应，通过氢化硅烷化、[4+2] cy … 更多加成等反应生成产物。通过这些研究，我们证明，在几种硅烯配合物上，金属-硅双键在诱导特定相互作用和重排方面发挥着重要作用，并产生了新型化学物质。首次合成了由硅、磷、铁组成的三元金属环，并对其结构、重排反应、二聚反应以及与各种极性分子的反应进行了研究。这些反应都伴随着硅磷键的断裂进行，可能是因为在这些金属环中，磷化物（亚硅基）配合物的典型形式的贡献很大，导致硅磷键的强烈极化，并且环应变激活了该键。在含有硫或碲而不是磷的体系中也观察到类似的金属环的形成和反应，而在含有氮的体系中，发现发生了涉及氨基甲硅烷基配体迁移到负原子上的有趣反应。较少的

项目成果

期刊论文数量（25）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Convenient preparation of Li[(η5-C5Me5)M(CO)2] (M=Ru, Fe) by the reaction of (η5-C5Me5)M(CO)2H with n-BuLi

通过(η5-C5Me5)M(CO)2H与n-BuLi反应方便制备Li[(η5-C5Me5)M(CO)2] (M=Ru, Fe)

DOI：
发表时间：
2002
期刊：
影响因子：
0
作者：
M. Okazaki;K. Satoh;T. Akagi;Masatoshi Iwata;Kyeong A. Jung;Rie Shiozawa;H. Okada;K. Ueno;H. Tobita;H. Ogino
通讯作者：
H. Ogino

Photochemistry of a Tellurosilyl(carbonyl)iron(II) Complex : Generation of a Novel Te-Si-Fe Three-Membered Cyclic Intermediate

碲甲硅烷基(羰基)铁(II)配合物的光化学：新型Te-Si-Fe三元环状中间体的生成