Exploring Equilibria between Aluminium(I) and Aluminium(III): The Formation of Dihydroalanes, Masked Dialumenes and Aluminium(I) Species

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.