卡宾镍、钯催化剂在共轭聚合物合成中的应用

项目名称： 卡宾镍、钯催化剂在共轭聚合物合成中的应用

项目编号： No.21304091

项目类型： 青年科学基金项目

立项/批准年度： 2014

项目学科： 数理科学和化学

项目作者： 史新翠

作者单位： 中国科学院长春应用化学研究所

项目金额： 25万元

中文摘要： 合成共轭聚合物的主要采用Kumada、Negishi、Suzuki、Stille及Yamamoto等过渡金属催化的碳-碳(C-C)偶联聚合反应。这类偶联聚合反应的催化剂主要是基于膦配体的镍（Ni）、钯（Pd）配合物。而无膦的氮杂环卡宾(NHCs)作为配体与过渡金属的键合而形成的过渡金属配合物的催化活性与三芳基膦很相似，又具有其独特的优势，例如，配体的立体和电子效应易于调节，能够与Ni、Pd形成很强的NHC-M键，不仅可以增加金属中心的氧化加成能力，而且能够阻止配体的解离，提高催化剂的稳定性。因此，本项目将设计与合成系列氮杂环卡宾及其Ni、Pd配合物，以Kumada和Suzuki聚合反应为研究对象，研究催化剂的位阻效应和电子效应对聚合反应的影响，发展用于共轭聚合物可控合成的新型催化剂体系，实现高分子量聚噻吩以及聚芴的高效合成。

中文关键词： 催化剂；交叉偶联聚合；共轭聚合物；活性链式聚合；

英文摘要： In the last twenty years, nickel and palladium-mediated cross-coupling reactions, including Kumada、Negishi、Suzuki、Stille and Yamamoto reaction, have played a crucial role in conjugated polymers (CPs) synthesis. Besides the nature of metal species, the steric and electronic properties of the ligands also make profound differences in the catalyst performance. With this in mind, we choose N-heterocyclic carbenes (NHCs) which behave like typical strong σ-donor ligands with negligible π-acceptor abilities as the ligands to synthesize varied nickel and palladium complexes. NHCs show superior performances in many aspects over traditional trialkyl- and triarylphosphine ligands. The following facts are responsible for the success of the ligands used in nickel and palladium-mediated cross-coupling reactions: enhancing the ability of oxidative addition; coordinating tightly to the metal central disfavoring cleavage; versatility of the steric and electronic properties;Herein, We focus on designing and synthesizing new nickel and palladium complexes based on the NHCs ligands. we will investigate the behaviors of these catalyst in the synthesis of the conjugated polymers with Kumada or Suzuki reaction. Through screening and optimizing the structure of catalyst, to understand influence of the catalyst structure on the polymeri

英文关键词： catalyst；cross-coupling polymerization；conjugated polymers；living chain-growth polymerization；