Phosphinidenoid metal complexes: structure, properties and reactions

本项目旨在开发M/ x -类膦金属配合物的化学性质。总的目标是确定这类新化合物与已建立的类碳化合物和类硅化合物之间的共性和差异，并进行系统的研究以阐明结构-性质关系。在第一个资助期的结果基础上，我们确定了6族金属弛豫配合物的溶剂分离离子结构，现在我们想研究过渡金属配合物碎片MLn、磷中心的取代模式和反离子性质对结构和反应性的影响。为此，我们计划，例如，合成非对映纯Li/X-类磷脂金属配合物，而不是外消旋Li/X配合物，或研究Mg/X和Cu/X配合物衍生物。特别重要的是这些新的P1构建块的探索性使用，以获得新的化合物类型，如：1)未连接的M/ x -类膦化合物，2)亲电末端膦烯金属(0)配合物，3)膦烯化合物，4)具有外环双键的高张力三元p -杂环，5)富磷配合物和6)磷-杂乙烯配合物。对异常键合情况（和反应途径）的理论分析将与L. Nyulászi/Budapest和A. Espinosa/Murcia合作进行，以进一步深入了解。

This project is designed to develop the chemistry of M/X-phosphinidenoid metal complexes. The general aim is to identify commonalities and differences between this novel class of compounds and well established carbenoids and silylenoids, and to carry out systematic studies in order to elucidate structure-property relationships. Based on results of the first funding period, where a solvens-separated ion structure for dileptic complexes of group 6 metals was determined, we now want to investigate the influence of the transition-metal complex fragment MLn, the substitution pattern at the phosphorus center and of the nature of the counter ion on structure and reactivity. To this end we plan, e.g., to synthesize diastereomerically pure Li/X-phosphinidenoid metal com-plexes, instead of the racemic Li/X complexes, or to study Mg/X and Cu/X complex derivatives. Of particular importance is the explorative use of these new P1 building blocks in order to access novel classes of compounds such as: 1) unligated M/X-phosphinidenoids, 2) electrophilic terminal phosphinidene metal(0) complexes, 3) phosphinidenes, 4) highly strained three-membered P-heterocycles with exocyclic double bonds, 5) phosphorus-rich complexes and 6) phospha-heterovinylidene complexes. The theoretical analysis of unusual bonding situations (and reaction pathways) shall be done in collaboration with L. Nyulászi/Budapest and A. Espinosa/Murcia to further in-depth insight.