Rationalising the Formation and Properties of Novel Main-Group Complexes Using Computational Methods

As the field of main-group chemistry generates compounds containing unusual structural motifs, novel bonds, and non-trivial oxidation states, computational methods are required to gain an in-depth understanding of these systems. This thesis describes the use of these methods on five experimental investigations, leading to the rationalisation of products formed through multiple theoretical techniques. Additionally, reaction profiles are generated to elucidate mechanisms and highlight key intermediates and transition states. Finally, driving forces for product formation are investigated through aromaticity calculations, resulting in the observation of multiple main-group complexes displaying aromaticity – a feature usually seen in organic systems.