This thesis investigated the reactivity of aluminium complexes towards furans in catalysed and uncatalysed reactions that break carbon-oxygen bonds. New types of reactions are reported that form ring-expanded products with insertion of the aluminium reagent into the heterocyclic ring. It was demonstrated that the selectivity of ring-expansion could be controlled by the presence of catalytic [Pd(PCy3)2]. The mechanisms of these C–O bond cleavage reactions were probed experimentally and computationally. The uncatalysed reactions were found to operate via a two-step pathway with electronic control over selectivity. In the catalysed reactions the pathway was found to operate via initial C–H activation of furan and subsequent C–O activation by a heterobimetallic Pd–Al complex.
In addition, the reactivity of a low-valent aluminium complex with anisoles was investigated. Both palladium catalysed and uncatalysed reactions were discovered and led to either sp2 C–O or sp3 C–O bond cleavage products, respectively. The mechanism of the uncatalysed reaction was probed experimentally and computationally to reveal an SN2 mechanism that may be operating via a Lewis acid-assisted transition state, or by the potential formation of a known aluminyl anion in-situ, in a base-catalysed process. Investigations into the late-stage functionalisation of anisole derivatives relevant to pharmaceuticals were carried out.
Furthermore, attempts to develop a new route to low-valent ß-diketiminate (BDI) aluminium complexes was investigated. It was shown, contrary to literature, that aluminayclopropenes can serve as “masked” sources of low valent aluminium by reversible alkyne binding. A computational study demonstrated the potential utility of this method for the generation of synthetic variants based on structural changes about the ß-diketiminate ligand. Efforts were made towards the isolation of masked low valent aluminium complexes with varied and novel BDI ligands.