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

制备了新型含共轭π配体的金属有机配合物，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，合成了含天青烯或戊二烯的多核Ru簇合物，其中一些被证明可以很容易地活化分子氢或氢硅烷。桥式共轭π-体系的亲和性变化可以从二铁或二Ru化合物的触变重排或二、三、四钚簇合物的氢化产物分析中得到证实。有机硅烷的H-Si键易被激活，导致了羰基化合物的硅氢化，缩醛和环醚的还原硅基化，环醚和硅氧烷的开环聚合。其次，新合成了高活性的有机铀酰胺类化合物，并从实验上证明了酰胺类配体的配位柔性。高反应…这些新化合物的活性更高，有助于几种有机底物的简单活化，包括亲核试剂的催化烯丙化反应。通过与一种有机钚物种的反应，合成了一种新型的含桥酰亚胺配体的二Ru配合物。第三，研究了磺酰胺类配体在钛化合物中的配位行为，为研究磺胺类配体的配位柔性提供了重要方面。实现了乙烯的聚合。第四，铜-联吡啶配合物催化合成多卤代γ-内酰胺类药物。系统地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。这些结果为均相催化碳-碳键形成反应及相关反应的发展提供了新的思路，其中配位柔性诱导π-配体的简单亲和性变化是发现新催化剂和新催化反应的重要线索。较少

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