过渡金属参有机反应机理的理论研究.pdf

摘要 以上工作中均采用理论计算方法对反应机理细节及其内在规律性进行研究， 在理论结果与实验数据实现良好匹配的情况下，验证了理论方法在反应机理研究 中的可行性，也为人们提供了很多其他实验方法无法获得的机理信息，例如关键 中间体、过渡态的结构以及直观形象的机理图像等。本论文的研究成果有望为我 们未来设计和开发新的金属有机化学反应及新催化体系提供理论支持与指导。 关键词：密度泛函方法 机理研究 偶联反应 二胺化反应 电子态间穿越点 过 渡金属 I ABSTRACT The recent development of quantum chemistry and theoretical methods enables the deep understanding of the detailed mechanism of organic reactions. This thesis mainly focuses on the mechanistic studies on transition metal complexes mediated organic reactions. The main contents include: Chapter 1 gives a brief introduction to different methodologies used in mechanistic studies of organic reactions. Chapter 2 mainly reviews the recent development in mechanistic studies of Cu(I) catalyzed C-X cross coupling reactions. Chapter 3 to Chapter 5 described the research topics of the mechanistic studies on transition metal mediated organic reactions, which were accomlished in my PhD studies in USTC. In Chapter 3, we mainly focus on the theoretical studies on Cu(I) catalyzed highly selective C-X (X=N, O) cross coupling reactions of aminoalcohols with arylhylides. With the aid of DFT (B3LYP) calculations, we are able to compare the energy demands of different pathways quantitatively and finally summarized the energetically most favorable one. On the basis of the electronic and structural analysis of the key intermediates and transistion states, we futher clarified the intrinsic releationship between the electronic character of ligand and the C-X coupling selectivities. This paper is published on J. Am. Chem. Soc.