Activated Anionic Aluminium For Synthetic Design, Catalytic and Energy Storage Applications

In the medium- to long-term it is highly important that society lessens its reliance on the rare, expensive, often toxic transition metals. To do this alternative strategies must be developed which can replicate or improve the desired outcomes but by judiciously using cheaper, more environmentally benign starting materials and reagents. Such a philosophy lies at the heart of this project, which will aim to develop the chemistry of the most abundant metal in the Earth's crust, namely aluminium, towards achieving some of these goals. A pertinent approach to enhancing the reactivity of aluminium compounds is to activate it in conjunction with a second metal, giving an anionic aluminium complex (a so-called 'ate'). Magnesium (the sixth most abundant metal in the Eart's crust) is one such metal which is known to accomplish this activation. This project will take a systematic approach to the refined synthesis of a library of magnesium aluminates and will characterize the resulting products fully across the three phases (solid, X-ray crystallography; solution, NMR studies; gas phase, DFT calculations). The application of these novel magnesium aluminates will then be advanced in three targeted areas.

Magnesium aluminates are primed to replace lithium centred materials for use as electrolytic material in rechargeable batteries. Unfortunately a lot of the material is wasted and the active species themselves are often poorly understood. By tuning the make-up of the aluminate, particularly with respect to the organic ligands which if too nucleophilic can attack the battery cathode, the well-defined novel complexes will be appraised for their utility as such an electrolyte.

Magnesium aluminates have also been identified as effective reagents in iron catalyzed bond forming processes but little is known about the intermediates of such reactions with current emphasis being placed on the final product itself. By peering in to this intermediary black box, this project will reveal what is hidden inside and previously unseen, allowing a far greater understanding of the processes involved and arming catalytic practitioners with far more details and knowledge with which to rationally develop the field. Iron, as the second most abundant metal after aluminium, demands greater attention in this area.
Finally, the products will be used as starting materials for the development of hydrogen rich supramolecular cluster compounds, which will be studied as model compounds on the road to preparing a reversible hydrogen storage system for portable energy applications. Ultimately, these branches of research will develop the practical applications of activated anionic aluminates with long-term sustainability at the forefront and will promote a step change in the way we understand metal promoted processes.

The multi-faceted approach to this project will ensure that its impact is felt in as wide a landscape as possible, covering multiple areas of practical importance such as energy storage, catalysis and materials chemistry. By utilizing inexpensive and sustainable metals, the impact will be felt over the long term as well as the short term. Research which contributes towards the development of cheaper forms of energy, or more energy efficient chemical transformations, are particularly timely given the current focus on rising domestic energy prices. Any spin-out companies resulting from the research will contribute towards wealth generation and employment. The host institutions recent award of 2013 Entrepreneurial University of the Year emphasizes the ease with which this form of impact can be obtained.
By improving bond forming processes through the use of cheaper more sustainable metals, the research and its outcomes will be of high value to many branches of the industrial sector, including those who are involved in the preparation of pharmaceuticals, fine chemicals and agrochemicals. Progress in energy storage will also be of value to the energy industry and, by association, to consumers in general.

The importance of the proposed research is emphasized by its alignment to EPSRC key research areas of catalysis, chemical structure, energy storage, hydrogen and alternative energy vectors, materials for energy applications, synthetic coordination chemistry and synthetic supramolecular chemistry.
SDR has a strong network of support in place in order to maximize the impact of this research, both at institutional level and also via his Fellowship sponsor, the Royal Society of Edinburgh, who excel in dissemination of scientific achievement to as wide an audience as possible.