White Phosphorus Activation by Indyl Anions

<p dir="ltr">The research described in this Thesis covers the synthesis of 8 new xanthene-based indyl anions. This includes the first example of indium anions supported by all group 1 metals (Li-Cs). The differences in their structural forms have been investigated, as well as their reactivity towards the activation of white phosphorus.</p><p dir="ltr">Chapter One provides a targeted literature review of the group 13 anions, specifically, the aluminyl anion and indyl anion and their reactivity towards small molecule activation and metal-metal bond formation. The Chapter concludes with a targeted review of the low-valent group 13 metal complexes towards white phosphorus activation.</p><p dir="ltr">Chapter Two extends the family of indyl anions by synthesising various ligand systems with varying degrees of steric bulk. During the synthesis of the first indyl anion in this Thesis, a new method of synthesising the indyl anion via a salt metathesis reaction was discovered, providing access to the low-valent anionic indium complexes without the requirement for harsh reducing agents.</p><p dir="ltr">Chapter Three investigates the new salt metathesis method to synthesise the series of alkali metal (Li-Cs) supported indyl complexes. However, this method was unsuccessful for the lithium and caesium indyl anions. An alternative metathesis reaction with the lithium and caesium iodides was found to react with the potassium indyl which facilitated access to the lithium and caesium indyl anions.</p><p dir="ltr">Chapter Four details the isolation of the series of indyl anions with increased stability through the coordination of TMEDA to the group 1 counter ion. Structural comparisons were made between the TMEDA-group 1 (Li-Rb) indyl complexes, before exploring their ability to reduce white phosphorus.</p><p dir="ltr">Chapter Five provides a comparative study of the first ‘stable’ indyl anion synthesised in this Thesis with unsaturated bonds and the chalcogenides, aiming to compare the isolated products to those of the aluminyl anion. The results in this Chapter further highlight the reactive capabilities of the indyl anion and how it may react as a heavy aluminyl anion analogue.</p>