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

具有双配位磷原子的膦离子具有独特的路易斯比亲和性，这使得合成新的磷基材料成为可能，并在合成和催化方面得到了广泛的应用。为了将膦盐的潜力扩展到创新领域，如离子液体中的反应或制备π导电材料，需要新型的磷阳离子，这些阳离子既表现出最佳的稳定性，又表现出缺电子磷原子与共轭多键体系的有效相互作用。该项目寻求加入两个申请者的研究小组分别在合成和计算化学领域的专业知识，以追求此类阳离子的发展。在这一方法中，计算方法与先进的合成方法的结合对于创造关于目标物种的电子结构的新知识至关重要，并通过允许实验研究的系统指导而产生协同效应。挑战在于开发可能参与单电子转移过程的新型芳香膦离子及其络合物，表征这些物种的氧化还原行为，以及作为进一步应用的先决条件对其电子和化学性质进行彻底的了解。

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.