廉价金属配合物催化C=C双键氢化反应的理论研究

It is a hot field in chemistry to substitute noble metal catalysts by cheap metal catalysts. With the development of theoretical & computational chemistry, catalytic chemistry and computer technology, it is possible to design new molecules with high activities based on structures and reaction mechanisms of catalysts. The goal of this project is to explore fundamental chemistry of discovering cheap metal catalysts for asymmetric hydrogenation of C=C bond (AHCC) gaining more value-added organic molecules. This project is trying to perform a systemic theoretical study on AHCC catalyzed by cheap metal complexes (CMCs) using quantum chemical method etc. It could be divided into several sections as the following: (a) the reaction mechanisms of different types of CMCs at multiple spin states and reaction modes of different C=C substrates (including functionalized and unfunctionalized substrates owning C=C bonds) with CMCs; (b) the electric and steric effects of metals and ligands in AHCCs; (c) the chemselectivity of CMCs in the hydrogenation of C=C, C=N and C=O bonds; (d) the nature of enantioselectivity in AHCCs; (d) the establishment of quantitative structure activity (or enantioselectivity) relationship (QSAR or QSER); (e) the design of active and enantioselective CMCs in AHCCs. This project could not only enrich the theoretical knowledge in asymmetic transition-metal catalysis, but also shed a light on the design of organometallic catalysts facilitating the hydrogenation of C=C bond.

用廉价金属替代贵金属，开发高活性高选择性催化剂，是化学领域的研究热点之一。本课题拟采用量子化学等方法研究不同类型廉价金属配合物催化C=C双键氢化反应机理，讨论催化剂在氢化不同C=C双键底物的作用机制，揭示催化剂金属中心及配体在不对称C=C双键氢化反应中的调变规律与本质，探讨催化剂催化C=X(X=C,N,O)选择性氢化规律，力图找出廉价金属催化不对称C=C双键氢化反应的关键特征，建立不对称C=C双键氢化反应的立体选择性规律，构建催化剂结构与性能的定量构效关系，系统结合以上不同因素对廉价金属配合物催化C=C双键氢化反应的活性和选择性的影响，设计具有潜在工业催化意义的新型高活性高选择性不对称C=C双键氢化廉价金属催化剂。这一课题的完成不仅丰富过渡金属不对称催化的理论基础，而且为基于催化剂结构及反应机理的不对称过渡金属催化剂的分子设计提供新的思路，并促进有机化学相关交叉学科的发展。

本课题采用量子化学等方法研究不同类型廉价金属配合物催化C=C双键氢化反应机理，讨论廉价金属催化剂在氢化不同种类底物的作用机制，研究底物中不同官能团对其催化活性及选择性的影响；调变金属中心与配体，明晰催化剂中金属中心及配体在不对称C=C双键氢化反应中调变规律和本质；比较不同价态金属中心对催化氢化反应机理的影响；探索廉价金属配合物催化C=C双键选择性氢化规律；构建该反应体系的催化剂结构-性能的定性定量构效关系；揭示廉价金属催化不对称C=C双键氢化反应的关键特征，建立廉价金属配合物不对称催化氢化反应的立体选择性规律；系统结合以上不同因素对廉价金属催化剂催化C=C双键氢化活性和选择性的影响，改性设计具有潜在工业催化意义的新型不对称C=C双键氢化廉价金属催化剂。

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