Phosphinidenoid metal complexes: structure, properties and reactions

该项目旨在发展M/X-亚膦金属络合物的化学。总体目标是确定这类新化合物与公认的卡宾和硅烯类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。根据第一个资助期的结果，确定了6族金属疏水络合物的溶剂分离离子结构，现在我们想要研究过渡金属络合物片段mln、磷中心的取代方式以及反离子的性质对结构和反应活性的影响。为此，我们计划合成非对映纯的Li/X-亚膦金属络合物，而不是外消旋的Li/X络合物，或者研究镁/X和铜/X络合物的衍生物。特别重要的是这些新的P1构筑块的探索性使用，以获得新的化合物类别，例如：1)未连接的M/X-亚膦化合物，2)亲电末端亚膦金属(0)配合物，3)亚膦化合物，4)具有外环双键的高应变三元P-杂环，5)富磷配合物和6)磷杂亚叉配合物。异常成键情况(和反应路径)的理论分析应与布达佩斯的L.Nyulászi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.