烯烃与CO2羰基酯化反应的非贵金属催化剂及过程调控研究

Alkoxycarbonylation of alkenes with CO2 has being expected to become a new green technology of carboxylic ester production. The disadvantage of the current studied catalytic system such as high cost and limited applicability made us to develop new protocol by implying cobalt, which is comparable cheap but rich in redox property, as the catalyst. In this project, the low-valent Co catalyzed Alkoxycarbonylation of alkenes with CO2 was taken as the object. The proposed studies include: explore and discover the elementary reaction in the activation/transformation of each substrate (e.g., alkanols, olefins, CO2), and provide quantitatively kinetic data and control law of some important elementary reactions; Focus on control law of the cationic counter-ion and ligand structure in the Co complexes on the key elementary or unit reactions; discover the route of formation and transformation of Co-H active intermediate and the respective kinetics; analysis of the transition state structure of insertion either CO2 or olefin into transient Co-H bond and disclose their mutual competitive mechanism; clarify the catalytic mechanism of low-valent Co catalyzed alkoxycarbonylation of alkenes with CO2. Based on the new theory and new mechanism to design a new catalytic system and provide a new technology in the synthesis of organic carboxylic ester.

以CO2为羰源的烯烃的羰基酯化反应，有望成为生产有机羧酸酯的一项绿色新技术。针对现有研究中成本高、普适性有限等问题，结合非贵金属Co价格低廉且氧化还原价态丰富的特点，本项目以构筑烯烃与CO2羰基酯化反应的非贵金属Co催化体系为目标，探索、发现各底物分子（如：有机醇、烯烃、CO2）活化及相关转化的基元反应，并提供一些重要基元反应的定量动力学数据和控制规律；重点研究低价金属Co离子型配合物中阳离子、配体结构对基元/单元反应的影响规律；揭示Co-H活性中间体形成/转化途径及其动力学规律；结合量子化学计算剖析烯烃及CO2插入中间体Co-H键的过渡态结构和竞争机制，阐明低价Co催化烯烃与CO2羰基酯化反应机理；基于新理论和新机理设计新型催化体系，为有机酯生产提供新技术。

以CO2为羰源的烯烃的羰基酯化反应，有望成为生产有机羧酸酯的一项绿色新技术。针对现有研究中成本高、普适性有限等问题，结合非贵金属Co价格低廉且氧化还原价态丰富的特点，本项目以构筑烯烃与CO2羰基酯化反应的非贵金属Co催化体系为目标，探索、发现各底物分子（如：有机醇、烯烃、CO2）活化及相关转化的基元反应。合成了20种金属Co配合物，采用原位制备的方法，研究低价Co在上述基元反应中的催化活性，同时合成了3中Ru配合物，与Co的催化活性进行比对。重点研究研究了MH活性中间体形成/转化途径及其动力学规律；结合量子化学计算剖析烯烃及CO2插入中间体MH键的过渡态结构和竞争机制，阐明Co/Ru催化烯烃与CO2羰基酯化反应机理；基于新理论和新机理设计新型催化体系，为有机酯生产提供新技术。