Oxidation and electrophilic modification of polypnictogen complexes

本项目旨在通过单电子氧化反应或与从多烟原配合物（En配体配合物；E = P - Bi）开始的阳离子亲电试剂的反应，在过渡金属配位球中形成和稳定前所未有的无取代多烟原阳离子。通过选择合适的氧化剂、合适的反应介质和稳定的弱配位阴离子，可以抑制络合物的形成，并且在氧化反应中，通过E-E键的形成或通过En-重组和-聚集，可以得到种类繁多的新的多烟原阳离子。作为多阳离子结构的一种替代方法，与阳离子亲电试剂的反应将开辟通往大型阳离子多烟原聚集体的途径，这些聚集体代表着与所选择的亲电试剂相对应的前所未有的混合主族元素链和笼状化合物。通过使用这两种方法，砷和锑的阳离子化合物可以大规模地获得，因为这样的例子到目前为止是相当已知的。该项目的一个特别重点将放在选定的阳离子产物的亲核衍生化上，以在产生的衍生物中建立各种各样的元素序列，并为生成有机烟原化合物开辟新的途径。所有产物的伴随研究，特别是反应途径，将使用DFT方法进行，以深入了解正在进行的反应，形成途径以及产物的成键关系。

The present project aims at the formation and stabilization of unprecedented substituent-free polypnictogen cations in the coordination sphere of transition metals via one-electron-oxidation reactions or reactions with cationic electrophiles starting from polypnictogen complexes (En ligand complexes; E = P – Bi). Hereby the use of En ligand complexes of the heavier homologues is focused with E = As and Sb. By selecting suitable oxidation agents, suitable reaction media and the stabilizing, weakly coordinating anions, the formation of complex compounds is hampered, and in oxidation reactions, by either E-E bond formations or by En-reorganizations and –aggregations, a large variety of new polypnictogen cations are obtained. As an alternative approach to polycationic structures, reactions with cationic electrophiles will open up the route to large cationic polypnictogen aggregates, which represent, corresponding to the chosen electrophile, unprecedented mixed main group element chains and cage compounds. By using both methods, cationic compounds of arsenic and antimony are accessible on a large scale, since such examples are fairly known so far. A particular focus of the project will lie on the nucleophilic derivatisation of selected cationic products to establish a large variety of sequences of elements in the resulting derivatives and opens new ways for the generation e.g. of organopnictogen compounds. Concomitant studies of all products, but in particular of the reaction pathways, will be carried out using DFT methods to gain profound insights into the reactions going on, the formation pathway as well as into the bonding relations of the products.