Sustainable catalysis enabled by first-row complexes displaying enzyme-inspired features (SUSCATYME)

The SUSCATYME project aims to develop sustainable approaches in catalysis by merging two largely unexplored concepts. Original supramolecular ligands will be prepared that include a catalytically active site formed by a first-row transition metal complex derived from Fe, Ni, Co, or Cu, while a substrate recognition site will be placed at a precise distance to reach a given selectivity in the substrate. The substrate recognition site, made from a zinc porphyrin, will enable the dynamic interaction of challenging nitrogenous substrates, ensuring enzyme-like characteristics such as increased substrate molarity around the active site and precise pre-organization of the substrate to achieve specific regio- and chemo-selectivities.^[1] Consequently, this enzyme-inspired approach is expected to enhance both the activity and selectivity of first-row transition metal complexes, which are generally deactivated in the presence of nitrogenous substrates. The nitrogen-containing compounds that could be functionalized by this approach are key constituents for the pharmaceutical industry and also pertain to material science with dedicated properties. The use of very inexpensive, abundant, biologically compatible, and cheap metals represents a significant advancement in a context that aims to avoid the use of noble, scarce, and toxic metals such as palladium or rhodium. The coordination of such metals will be achieved through the use of polyazamacrocyclic ligands (such as cyclam and cyclen), whose properties can be easily tuned by the selection of appropriate coordinating side arms and/or scaffold modifications.^[2] Such ligands have been extensively used in the last decades in the medical field as chelators for metallic cations relevant to medical imaging (MRI, PET… ) or radiotherapy, but their use in catalytic applications remain scarce.

^[1] R. Gramage Doria et al., Angew. Chem. Int. Ed. 2021, 60, 18006-18013; ACS Catal. 2023, 13, 7715–7729; Chem. Sci. 2024, in press, DOI : 10.1039/D4SC01515K.

^[2] T. Troadec et al., Chem. Sci., 2024, in press; Inorg. Chem. 2023, 62(21), 8112–8122; Org. Biomol. Chem., 2024,22, 3059-3067

https://gramagedoria-lab.com/

https://www.univ-brest.fr/cosm/fr/page/macrocycle-azotes-et-coordination

The candidate must hold a Masters degree (or equivalent) and have experience in Synthesis and molecular chemistry. Additional skills in coordination chemistry and/or catalysis are strongly appreciated.