高活性、高稳定性的炔烃复分解催化剂的设计、合成以及在共轭高分子合成中的探索研究

Olefin metathesis has achieved great success in the polymer synthetic chemistry and synthetic organic chemistry, comparatively speaking, alkyne metathesis research behind a lot. Alkyne metathesis has became very important research area in the polymer chemistry and organic synthesis. This project focused on the design and synthesis of the alkyne metathesis catalysts with both high catalytic activity and robustness to air and moisture at the molecular level, and then applied them to a new type of organic synthesis and high performance, structurally controlled polymer synthesis. Primarily through the rapid screening the good catalyst with high catalytic activity, good functional group tolerance, high selectivity will be developed. Then several highly efficient, easy synthesis, a wide range of applications Schrock-type [M ≡(E) X3, M = Mo, W; E = CR, N] catalyst and more practical, new high oxidation state ruthenium carbyne catalyst [Ru ≡ (CR) X3] will be achieved allow for fine-tuning of their steric and electronic properties in order to further optimize their stability and catalytic performance. The good candidate will be tested for the formation of carbon-carbon triple bond of the polymer material and organic synthesis, such as ring-opening alkyne metathesis polymerization (ROAMP), ring-closing alkyne metathesis ((RCAM)) as well as acyclic diyne metathesis (ADIMET). The study also will further reveal the mechanism of alkyne metathesis reaction.

烯烃复分解反应在高分子合成化学和有机合成化学中已取得巨大成功，相比较而言，炔烃复分解反应研究落后很多。炔烃复分解反应在高分子合成化学和有机合成化学等方面具有非常重要的意义，本项目主要集中在具有高活性、高稳定性的炔烃复分解催化剂分子水平的设计和合成并将其应用于新型的有机合成和具有高性能、结构可控的高分子合成中。主要通过在分子水平设计催化剂，快速筛选出具有高催化活性、较好的官能团容忍性、高选择性的催化剂，利用电子和立体的精心调控得到数系列催化剂，从中优选出几种高活性、易合成、高稳定性、应用范围广的类Schrock 卡拜[M≡(E)X3， M = Mo，W；E = CR，N]催化剂和高氧化态的新型钌卡拜[Ru≡(CR)X3]催化剂，并将其应用于开环炔烃复分解聚合反应（ROAMP）、闭环炔烃复分解（RCAM）以及非环二炔烃复分解聚合反应（ADIMET）中，进一步诠释炔烃复分解反应的机理和反应历程。

烯烃复分解反应在高分子合成化学和有机合成化学中已取得巨大成功，相比较而言，炔烃复分解反应研究落后很多。炔烃复分解反应在高分子合成化学和有机合成化学等方面具有非常重要的意义，本项目主要集中在具有高活性、高稳定性的炔烃复分解催化剂分子水平的设计和合成并将其应用于新型的有机合成和具有高性能、结构可控的高分子合成中。项目建立和发展高催化活性、高稳定性的催化聚合反应，探讨反应进行的机理，并揭示金属催化剂在新型共扼高分子反应中的作用。合成了具有具有较好的光、电、热性能的新型高性能高分子材料。项目的完成为发展炔烃复分解催化剂和新型高性能高分子材料提供理论指导，得到具有创新性的研究结果，该研究既丰富了炔烃复分解和高性能高分子材料化学，又拓宽了具有较好的光、电、热性能的新型高性能高分子材料的应用。