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Exploration of novel organometallic compounds bearing conjugate π-ligands and their applcation to catatitic homogeneous carbon-carbon bond forming reactions and related reactions

具有共轭π配体的新型有机金属化合物的探索及其在催化均相碳-碳键形成反应及相关反应中的应用

基本信息

批准号：
10450343
负责人：
NAGASHIMA Hideo
金额：
$ 2.94万
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：
1998
资助国家：
日本
起止时间：
1998 至 2000
项目状态：
已结题

项目摘要

Preparation of new organometallic complexes bearing conjugate π-ligands was achieved, which showed unique catalytic reactivity in homogeneous carbon-carbon bond forming reactions and related reactions. First, multinuclear ruthenium clusters bearing azulenes or acenapthylenes were synthesized, some of which were proved to achieve facile activation molecular hydrogen or hydrosilanes. Hapticity change of the brigding conjugate π-systems was evidenced in either the haptotropic rearrangements of diiron or diruthenium compounds or in the product analysis of hydrogenation of di-, tri-, or tetraruthenium clusters. Facile activation of the H-Si bond of organosilanes led to catalytic hydrosilylation of carbonyl compounds, reductive silylation of acetals and cyclic ethers, ring-opening polymerization of cyclic ethers and siloxanes. Second, highly reactive organoruthenium amidinates were newly synthesized, and coordinative flexibility of the amidinate ligands were proved experimentally. High react … More ivity of these new compounds were useful for facile activation of several organic substrates including catalytic allylation of nucleophiles. The reaction with an organoruthenium species led to novel type of diruthenium complexes bearing bridging amidinate ligands. Third, coordination behavior of sulfoamide ligands was examined in titanium compounds, which provided important aspects in coordinative flexibility of the sulfoamide ligands. Polymerization of ethylene was accomplished. Forth, polyhalogenated γ-lactams were catalytically synthesized by copper-bipyridine complexes. Systematic investigation on electronic and steric properties of either the bipyridine ligands or the substrates contributes to better understanding of the catalysis. These results provided new concepts for the development of homogeneous catalytic carbon-carbon bond forming reactions and related reactions, in which coordinative flexibility inducing facile hapticity change of the π-ligands is an essential clue to discover new catalysts and new catalytic reactions. Less

合成了一类新型共轭π配体金属有机配合物，在均相碳-碳键形成反应及相关反应中表现出独特的催化活性。首先，合成了多核钌簇合物，其中部分钌簇合物被证明可以容易地活化氢分子或氢硅烷分子。桥共轭π-系统的Hapticity的变化被证明在haptotropic重排的二铁或二钌化合物或在氢化的二，三，或四钌簇的产物分析。容易活化的H-Si键的有机硅烷导致羰基化合物的催化氢化硅烷化，缩醛和环醚的还原硅烷化，环醚和硅氧烷的开环聚合。第二，合成了高反应活性的脒基钌配体，实验证明了脒基钌配体的配位灵活性。高反应 ...更多信息这些新化合物的活性可用于几种有机底物的容易活化，包括亲核试剂的催化烯丙基化。与有机钌物种的反应导致新型的双钌配合物轴承桥接脒配体。第三，研究了磺酰胺配体在钛化合物中的配位行为，为磺酰胺配体的配位灵活性提供了重要方面。完成了乙烯的聚合。第四，研究了铜-联吡啶配合物催化合成多卤代γ-内酰胺。系统研究联吡啶配体或底物的电子和空间性质有助于更好地理解催化作用。这些结果为发展均相催化碳-碳键形成反应及相关反应提供了新的思路，其中π-配体的配位柔性导致的不规则性变化是发现新催化剂和新催化反应的重要线索。少