Stabilisation and Reactivity of Phosphenium Ions with Extended pi-electron Systems

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Phosphenium ions with a two-coordinate phosphorus atom exhibit a unique Lewisambiphilic reactivity which has enabled the syntheses of new phosphorus based materials and was employed in various applications in synthesis and catalysis. To extend the potential of phosphenium salts to innovative areas such as reactions in ionic liquids or the preparation of π-conducting materials, new types of phosphorus cations are needed which exhibit both optimum stability and efficient interaction of the electron deficient phosphorus atom with conjugated multiple bond systems. This project seeks to join the expertise of the research groups of the two applicants in the fields of synthetic and computational chemistry, respectively, to pursue the development of such cations. The combination of computational with advanced synthetic methodology is in this approach essential for the creation of new knowledge on the electronic structure of the target species and produces synergisms by allowing a systematic direction of the experimental research. Challenges lie in the development of new types of aromatic phosphenium ions and their complexes which may participate in singleelectron transfer processes, the characterisation of the redox behaviour of these species, and the development of a thorough understanding of their electronic and chemical properties as precondition for further applications.