钌促进的氮杂环卡宾分子内c-h键活化与相关反应分析-ruthenium - promoted activation of c - h bond in nitrogen heterocyclic carbene molecule and analysis of related reactions.docxVIP

中文摘要中文摘要本文设计合成了多个系列的氮杂环卡宾配体及相应的钌配合物，研究了钌 中心促进的分子内C-H键活化，这些结果有助于进一步研究钌促进的C．H键活 化在有机合成上的应用。通过一系列芳基与烷基取代的氮杂环卡宾与[p-cymene)RuCl2]2反应，得到 一系列芳基，烷基官能团化的(p-cymene)Ru(II)氮杂环卡宾配合物，其中包括 几个分子内C-H键活化的环金属化配合物。我们发现(p-cymene)Ru(NHC)体系 可以发生分子内sp2与sp3 C—H键的活化，经过深入系统地研究发现(矿 cymene)Ru(I I)氮杂环卡宾配合物分子内sp3比sp2 C—H键活化更容易进行。氮 杂环卡宾取代基的电子效应和体积效应以及环金属化后成环的大小等因素都对 分子内C-H键活化有很大影响。研究了含有茚基官能团的氮杂环卡宾及其前体与Ru3(CO)12的反应，直接 使用咪唑盐前体反应时得到单核钌配合物；而使用茚基官能团氮杂环卡宾反应 则得到双核与三核金属中心的簇合物，同时还伴随有多重分子内sp2和sp3 C．H 键活化。系统地研究了一系列不对称取代的氮杂环卡宾与Ru3(CO)12的反应，得到 单核，三核与四核的钌化合物，发现在这些反应过程中几乎都存在分子内C．H 键活化。其中氮杂环卡宾四核钌配合物是第一次在氮杂环卡宾钌簇合物化学中 发现。关键词：钌，C-H键活化，环金属化，氮杂环卡宾AbstractAbstractIn this dissertation，several series of N-heterocyclic carbene l i gands and their ruthenium complexes were designed and synthesized,and meir intramolecular C-_H bond activation behaviors were also studied，which could be helpful to further develop the application ofruthenium·-promoted C·-H bond activation in organic synthesis．The intramolecular spz and sp’C_H bond activated products as well as themonomctalated products based on the“p—cymene)Ru(NHC)”framework were synthesised by treatment of a series of the NHCs with[p-cymene)RuCl2]2 under mild conditions．A new NHC precursor Was also designed to compare the reactivity upon the sp2 and sp3 C-H bond activation process．Both electronic and steric effect of the N-heterocyclic carbene，as well as ring size of the cyclometal lated ruthenacycle were found to influence on the i ntramo l ecu lar C-H bond activation process．The reactions of indenyl-functionalized imidazolium salts and N-heterocycliccarbenes、Ⅳi也Ru3(CO)12 were studied．The normal mononuclear metal complexeswere obtained via direct reaction of indenyl·functionalized imidazolium salts withRu3(CO)12．Unexpected multiply intramolecular C-H activated dinuclear andtrinuclear clusters were obtained via thermal treatment of corresponding indenyl-functionalized N-heterocyclic carbenes with Ru3(CO)12．The reactions of a series of unsymmetrically substituted N·hete