项目名称： 基于醇分子C-C偶联的C-H键选择性操控的催化作用原理

项目编号： No.91545116

项目类型： 重大研究计划

立项/批准年度： 2016

项目学科： 数理科学和化学

项目作者： 陈加藏

作者单位： 中国科学院山西煤炭化学研究所

项目金额： 86万元

中文摘要： 精确操控C-H键直接构筑C-C键是一个富有挑战性的绿色化学课题。醇分子中存在C-H、O-H、C-O和C-C多个化学键，选择性操控C-H键直接构筑C-C键通常是相当困难的。我们前期的研究表明，光场和催化剂作用下，醇分子可在室温发生C-H键选择性断裂释放氢气，生成的碳自由基进而C-C偶联为邻二元醇，选择性可高达90%以上。此结果反映了精确操控醇分子C-H键是可行的。本项目将聚焦于醇分子C-H键选择性操控这一基础科学问题，通过考察光场和热场作用下醇分子在催化剂表面吸附和活化的差异性、催化剂表面组成和结构与醇分子吸附和活化以及C-C偶联之间的联系、反应中间体的结构和来源、反应介质的作用实质，认识光场之于C-H选择性断键的作用实质，认识光场作用下醇分子催化活化的特征以及催化作用机制，进而认识C-H键选择性活化或断裂的催化作用本质，为复杂体系中C-H键选择性操控和C-C键构筑提供科学依据。

中文关键词： 催化；醇；脱氢；碳-碳偶联；C-H键选控

英文摘要： The precise manipulation of organic C-H bonds for the direct construction of C-C bonds has emerged as an attractive and challenging goal in green chemistry and catalysis. For alcohol molecules, it is normally difficult to selectively manipulate the C-H bond, because different bonds, including C-H, O-H, C-O, and C-C bonds are involved in. From our previous studies, the direct dehydrogenation of alcohol molecules to selectively produce ortho-diol compounds is possible under the function of light and catalysts. This process, able to play very high selectivity, above 90%, reflect the possibility of the selective manipulation of the alcohol-involved C-H bonds. In this proposed subject, we will focus on the basic scientific question of how to precisely manipulate the C-H bond and try to understand the theoretical principle hidden behind the light-assisted catalytic selective manipulation of the C-H bonds. The studies would be performed from multiple aspects, such as the comparison of the light and heat effects on the alcohol-adsorption and chemical bond activation over catalyst surfaces, the understanding of the relationship between the catalyst surface structure and C-C coupling selectivity, tracing the source of the reaction intermediates and products, understanding the nature involved in the effect of reaction media, bond. This study is generally important in providing theoretical strategy for the catalytically selective manipulation of C-H bond in the bond-complex chemical systems.

英文关键词： catalysis;alcohol;dehydrogenation;C-C coupling;C-H manipulation