Open Shell d-Block Aluminium Bimetallics for Small Molecule Activation

Aluminium is one of the most abundant elements in the Earth's crust, and the most common metal, which makes it an excellent candidate for use in sustainable chemistry. Typically, it has been used in chemical laboratories and industries for its ability to accept electrons from other molecules. However, recent advancements have flipped this usual reactivity, allowing some negatively charged aluminium compounds to donate their electrons to other chemicals. This opened up the field of "aluminyl" (sometimes called alumanyl) chemistry, particularly following a landmark paper by Hicks, Vasko, Goicoechea and Aldridge.
Since this paper, much work has been done on how the aluminyl ions react and how they bond to metals, for example with copper, silver, gold and zinc. Aluminium is described as relatively 'electropositive', this means that the electrons in the metal-aluminium bonds will typically prefer to be closer to the other metal rather than aluminium. By pushing these electrons towards the bonded metal, it enhances how much it in turn can donate its electrons, making the metal more reactive. Examples of this chemistry include reactions with carbon dioxide, that show that the electrons have been donated from the metal, rather than from the aluminium. This chemistry represents one instance of how 'bimetallic' molecules (compounds with two metals in them) can have unique reactions that the
individual components are incapable of on their own.
My research will fall into this field. Bimetallic aluminyl compounds are still a rapidly growing area of study, and my project aims to expand this further into the top row of transition metals on the Periodic Table. For instance, iron is one such element, and is the most plentiful transition metal, and second only to aluminium in terms of all metal abundances. Therefore, using aluminium and iron together could offer a sustainable chemical solution that has the potential to be very reactive towards industrially relevant small molecules, for instance nitrogen (N2), hydrogen (H2), carbon monoxide (CO) or carbon dioxide (CO2). In summation, the project objectives include:
- Synthesis of new aluminyl-metal bonds.
- Optimise the synthesis and reactivity of these novel compounds, using different types of aluminyl sources.
- Testing the reactivity of these new compounds with industrially relevant small molecules, aiming to create value-added products.

As such, this project falls within the EPSRC 'Synthetic Coordination Chemistry' research area, as it tackles more fundamental molecule design and synthesis, to underpin future development, perhaps towards catalytically active molecules.