过渡金属催化的炔烃复分解反应

综述了过渡金属均相催化的炔烃复分解反应进展,主要分为两部分：一是炔烃复分解反应在炔烃合成中的应用,即从六、七十年代Mortreux催化剂的发现能均相催化炔烃的歧化反应,经过一系列的条件改造,合成了炔醚和二芳基乙炔等化合物,并提出了可能的两种机理：金属卡宾和金属卡拜机理;金属钼和钨的卡拜络合物相继合成,发现此类络合物能够催化官能化的二炔的复分解反应,合成一系列的大环化合物。二是炔烃复分解反应在合成高聚物中的应用,即钙和钨的卡拜络合物被用来催化ROMP和ADIMET反应合成高聚物,改良了的Mortreux催化剂也能催化高聚物的生成,这些高聚物在发光器件、有机"塑料"激光、液晶显示器上都有应用。

Transition metal-catalyzed alkyne metathesis reaction

This paper summarizes the development of transition metal-catalyzed alkyne metathesis reaction. It consists two parts: (1) Applications in the synthesis of alkynes In 60s～70s the Morterux-type catalyst was found to homogeneously catalyze the discrimination of alkynes. After a series of modifications of reaction conditions, alkynyl ethers and diaryl acetylenes were synthesized from two alkynes. Two palusible mechanisms, e.g., metallocarbene-type and metalocarbyne- type mechanisms were proposed. Molybdenum and tungsten-carbyne complexes were synthesized and used to catalyze the metathesis reaction of functionalized diynes to afford the corresponding carbon- carbon triple bond-containing macrocycles. (2)Applications in the synthesis of polymers Molbdenum and tungsten-carbyne complexes can catalyze the ROMP (ring-opening metathesis polymerization) and ADIMET ( acyclic diynes metathesis) to afford carbon-carbon triple bond- containing polymers. To circumvent the tedious preparation of carbyne complexes, new Mortreux-type catalyst was designed and synthesized to catalyze ADIMET. These polymers can be applied in light-emitting devices, organic "plastic" lasers and polariser in liquid crystal display screens.