3dMAmm - Harnessing earth-abundant 3d metals for ammonia activation and functionalization

The activation of the strong bonds found between atoms in small molecules (like ammonia), can be very efficiently achieved by 2nd and 3rd row transition metals in 2-electron transfer processes. For first row transition metals, the activation mechanisms are much less understood, and can vary between radical, one electron pathways, or significant participation of the ligand sphere surrounding the light metal centres in both redox-non-innocent and covalent binding pathways.However, the use of these metals is accompanied with the advantages of decreased costs and toxicity, as well as increased accessibility (more abundant and therefore inherently more sustainable), compared to the 4d and 5d metals. The drive to employ these light transition metals is therefore easily understood, but it is hampered by their complicated reactivity (which includes preparative reactivity).

This project aims to synthesize 3d transition metal complexes to activate the strong covalent bonds found in ammonia. Ultimate exploitation of this substrate in reductive catalytic reactions are targeted for the preparation of useful ‘everyday’ organic chemicals (building blocks of pharmaceuticals, agrichemicals, polymers, etc.). This will be done with the development of ligands that play a non-innocent, cooperative role in bond activation.