Documenting the synthesis and isolation of novel low oxidation state aluminium (Al) compounds, which until recently has seen relatively slow progress over the 30 years since such species were first isolated.

The design of new reductive routes to low oxidation state aluminium (Al) compounds offers the opportunity to better understand redox processes at the metal centre and develop reactivity accordingly. Here, a monomeric Al I compound acts as a stoichiometric reducing agent towards a series of Al III dihydrides, leading to the formation of new low oxidation state species including symmetric and asymmetric dihydrodialanes, and a masked dialumene. These compounds are formed by a series of equilibrium processes involving Al I , Al II and Al III species and product formation can be manipulated by fine-tuning the reaction conditions. The transient formation of monomeric Al I compounds is proposed: this is shown to be energetically viable by computational (DFT) investigations and reactivity studies show support for the formation of Al I species. Importantly, despite the potential for the equilibrium mixtures to lead to ill-defined reactivity, controlled reactivity of these low oxidation state species is observed.

The mechanism of the aluminum-mediated hydroboration of terminal alkynes was investigated using a series of novel aluminum amidinate hydride and alkyl complexes bearing symmetric and asymmetric ligands. The new aluminum complexes were fully characterized and found to facilitate the formation of the ( E )-vinylboronate hydroboration product, with rates and orders of reaction linked to complex size and stability. Kinetic analysis and stoichiometric reactions were used to elucidate the mechanism, which we propose to proceed via the initial formation of an Al-borane adduct. Additionally, the most unstable complex was found to promote decomposition of the pinacolborane substrate to borane (BH 3 ), which can then proceed to catalyze the reaction. This mechanism is in contrast to previously reported aluminum hydride-catalyzed hydroboration reactions, which are proposed to proceed via the initial formation of an aluminum acetylide, or by hydroalumination to form a vinylboronate ester as the first step in the catalytic cycle.

The design of new reductive routes to low oxidation state aluminium (Al) compounds offers the opportunity to better understand redox processes at the metal centre and develop reactivity accordingly. Here, a monomeric Al I compound acts as a stoichiometric reducing agent towards a series of Al III dihydrides, leading to the formation of new low oxidation state species including symmetric and asymmetric dihydrodialanes, and a masked dialumene. These compounds are formed by a series of equilibrium processes involving Al I , Al II and Al III species and product formation can be manipulated by fine-tuning the reaction conditions. The transient formation of monomeric Al I compounds is proposed: this is shown to be energetically viable by computational (DFT) investigations and reactivity studies show support for the formation of Al I species. Importantly, despite the potential for the equilibrium mixtures to lead to ill-defined reactivity, controlled reactivity of these low oxidation state species is observed.