Reactivity and redox behaviour of ferrocenyl substituted pnictogens and chalcogens

The molecular chemistry of low-valent cations of main group elements has sparked curiosity over the past decades, owing to their unique properties and the promise of a more abundant, cheaper alternative to transition metals in catalysis.
Combining low-valent main group cations with the fruitful chemistry of the iconic ferrocene, this thesis explores the use of the monodentate ferrocenyl (Fc) unit as a ligand in low-coordinate cations of group 15 elements and their derivatives. Additionally, it reports the preparation, structural and spectroscopical characterisation of ferrocenyl substituted pnictogens and tellurides, together with their redox properties. The triferrocenylpnictogens were studied in detail in order to understand the electronic coupling in electrochemically generated monocations.
The electron-rich nature of the Fc ligand allowed for the isolation and full characterisation of the diferrocenylpnictogenium ions. Their molecular structures revealed that such electrophiles are stabilised by intramolecular Fe…E (E = P, As, Sb, Bi) interactions, while still remaining Lewis superacids. The chemical reactivity of the diferrocenylphosphenium ion was investigated as well: the oxidative addition of diaryldichalcogenides, reactions with dienes, alkynes and allenes, and subsequent isolation of a Wheland intermediate of ferrocene all contribute to our understanding of the properties of such highly reactive species, and explore their potential in main-group catalysis.