Unconventional Phosphorus Ligands for Catalysis

磷（III）配体在均相催化的重要领域（例如氢甲酰化，氢氰化，C-C和C-N偶联反应，烯烃寡聚和复分解，不对称氢化）中表现突出，其中许多过程已经找到了工业应用。p -配体可以修饰的方便性和灵巧性是它们受欢迎的原因之一。传统的P-配体含有P-C， P- o或P- n键，但本项目的目的是通过探索含有P- f， P- b和P=C键的配体在均相催化中的应用来扩展P-配体空间的边界。这些化合物的合成近年来已有所发展，但其在催化方面的应用仍未开发。将研究的催化过程包括使用氟磷酸盐配体的氢甲酰化和使用钳形配体配合物的脱氢。尽管对N类似物（亚胺）的应用有很大的兴趣，但磷酸烯烃配体在学术上已经得到了广泛的研究，但还没有作为催化配体。二（磷酸烯烃）将筛选各种催化反应，包括甲氧基羰基化。

Phosphorus(III) ligands are pre-eminent in important areas of homogeneous catalysis (e.g. hydroformylation, hydrocyanation, C-C and C-N coupling reactions, olefin oligomerisation and metathesis, asymmetric hydrogenation) and many of these processes have found industrial applications. The facility and finesse with which P-ligands can be modified is one of the reasons for their popularity. Conventional P-ligands contain P-C, P-O or P-N bonds but the aims of this project are to stretch the boundaries of P-ligand space by exploring the use in homogeneous catalysis of ligands containing P-F, P-B and P=C bonds. The synthesis of these compounds has been developed recently but their applications in catalysis remains largely unexplored. The catalytic processes that will be investigated include hydroformylation using fluorophosphite ligands and dehydrogenation using pincer-ligand complexes. Phospha-alkene ligands have been extensively studied for academic interest but not as ligands for catalysis despite the great interest in the applications of N analogues (imines). Bis(phospha-alkenes) will be screened for a variety of catalytic reactions including methoxy-carbonylation.