挑战性羰基化合物的选择性催化氢化

项目名称： 挑战性羰基化合物的选择性催化氢化

项目编号： No.21472215

项目类型： 面上项目

立项/批准年度： 2015

项目学科： 数理科学和化学

项目作者： 韩召斌

作者单位： 中国科学院上海有机化学研究所

项目金额： 80万元

中文摘要： 羰基化合物如二氧化碳、碳酸酯、酰胺以及聚酯或聚酰胺等在温和条件下的催化氢化依然是氢化反应中的挑战性的课题。本项目拟以氢气为还原剂，研究惰性羰基化合物如二氧化碳、碳酸酯、酰胺、聚羧酸酯及聚酰胺等在金属络合物催化下的还原反应，将从具有双功能作用的催化剂的设计、合成入手，系统研究这些催化剂在上述挑战性羰基化合物的催化氢化反应中催化活性和选择性调控的规律，通过配体/中心金属/羰基化合物/氢气之间相互作用的实验和理论研究，深入理解配体的结构和催化剂的组成与催化效率和选择性控制之间的关系，开发一系列高效、高选择性催化剂，为多种不同类型挑战性羰基化合物的高选择性氢化提供创新的方法，为二氧化碳和羰基聚合物废弃物等碳资源的回收再利用提供新的解决方案。

中文关键词： 金属络合物；过渡金属催化；催化反应；反应性；构效关系

英文摘要： The hydrogenation of carbonyl compounds, such as CO2, carbonates, amides,polyesters and polyamides using molecular hydorgen under mild conditions represents one of the the challenging topics in catalytic hydrogenation reactions since their inherent chemical inertness of these molecules towards reduction. The aim of this project is to develop new catalytic systems for the reduction of above-mentioned challenging carbonyl substrates using molecular hydrogen as the reductant. This project will focus on the design and synthesis of some N-H moiety-bearing metal-ligand bifunctional molecular catalysts,as well as their catalytic performances and inherent regulation of selectivity control in homogeneous catalytic hydrogenation of the difficult carbonyl compounds mentioned above. Both experimental and computational approaches will be applied to proble the intricate interactions among ligand/metal/substrate/H2 components, in order to gain the valuable insightful understanding of the underlying relationship between the catalyst structures and the catalytic performances in the hydrogenation. The implementation of the proposed project will hopefully lead to the successful discovery of some novel catalytic systems, and provide the advanced innovative methogology for the hydrogenation of various challenging carbonyl compounds.In particular, the hydrogenation of carbon dioxide to methanol and the hydrogenative depolymerization of polyesters and polyamides provide a promising solution for recycling and reutilizing renewable carbon resource on the basis of an organometallic approach of catalysis.

英文关键词： metal complex;transition metal catalysis;catalytic reaction;reactivity;structure-reactivity relationship