Application of Phosphadiazonium Cations in Nitrogen-based Heterocycle Chemistry
Abstract
Phosphadiazonium cations capture the essence of phosphorus mononitride (P≡N), an extremely reactive molecule, as these compounds contain a P≡N moiety stabilized by a bulky aryl group. However, since being synthesized in the late 1980s by Niecke et al. their chemistry has remained a relatively niche field. Burford et al. reacted phosphadiazonium cations with nitrogen-centred Lewis bases to create a wide variety of interesting adducts ([L-PNMes*][OTf]). This thesis builds on the previous work and is focused on applying phosphadiazonium cations in nitrogen-based heterocycle materials chemistry. Reacting these compounds with chelating hydrazone ligands provides an interesting avenue for growth in this niche sector of materials chemistry and provides foundational work that can be built on moving forward. The novel pnictogen-rich heterocycles presented in this thesis display an interesting bonding arrangement studied through NMR spectroscopy, UV-Vis spectroscopy and using density-functional theory.