Oxidation and electrophilic modification of polypnictogen complexes

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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.