| Project Detail |
Metal-metal bonds for sustainable chemical processes
Demand exists for eco-friendly reagents in sustainable chemical processes. Despite the widespread use of transition metal-based catalysts, they are costly and toxic. Main group-based species with low oxidation states and/or metal-metal bonds are being explored as potential replacements. However, current examples are limited to molecules containing magnesium, leaving other s-block metal-metal bonds unexplored. In this context, the ERC-funded MeMe-BONDS project aims to engineer sustainable reductants using novel s-block bonds stabilised by adjustable electronic interactions. The project will integrate ligands with s-acceptor functionality to control the reactivity of formed radical intermediates and develop new s-block metal-metal bonds. It will employ a combination of experimental and computational methods to understand the electronic structures.
The increasing demand for environmentally friendly reagents to perform sustainable processes has become of paramount relevance for modern academia and industry. Transition metal-based catalysts are long-established players in many important chemical transformations, given their ability to cleave and form chemical bonds with facile oxidation state changes. Their high cost and/or toxicity, however, have prompted the search for potential replacements. The past decades brought fascinating discoveries of main-group-based species exhibiting low-oxidation states and/or metal–metal bonds with excellent and tunable reducing properties. Nonetheless, despite formidable efforts invested in broadening the scope, existing examples are restricted to Mg-containing molecules, while other s-block metal-metal bonds remain unaccomplished. MeMe-BONDS will address this challenge by engineering novel sustainable reductants based on hitherto unknown s-block bonds stabilized by tunable electronic interactions. This breakthrough will be possible by combining the steric shielding provided by commonly used ligands with the introduction of a s-acceptor functionality to tame the inherent reactivity of formed radical intermediates. This innovative metal-ligand interaction will allow for the precise incorporation of one or two extra electrons, resulting in a unique electronic structure, which - under suitable conditions - will afford the new s-block metal–metal bonds. Tandem experimental and computational methods will enable a fundamental understanding of the electronic structures and their interplay with the nature of the substituents. The properties and reactivity of these novel bonds will be thereby tuned, opening the door for application in small molecules’ activation and as electronically versatile catalysts. The output of this project will enrich the synthetic chemistry toolbox and pave the way for more environmentally friendly chemical processes. |
