Demonstrating and Utilizing Cooperativity in Catalytic Transformations of Small Molecules by Rigidly Linked Multinuclear Assemblies

Project: Research

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The use of carbon dioxide as a non-toxic C1 building block and its valorization into useful chemical feedstock and materials are desirable, due to its inexpensive, abundant and sustainable nature. Metal-metal cooperativity in multinuclear systems is an established bioinspired strategy in catalyst design, but such reactivity can frequently be impeded by flexible ligand structures or direct metal-metal interactions. Here, a design approach based on bimetallic frameworks derived from cofacial metal-ligand subunits, which are tethered by an inflexible backbone moiety to inhibit M···M bonding, is proposed. These rigidly linked structures afford minimal lateral displacement but allow axial rotation of the metal-ligand components, so that their relative spatial arrangement and orientation (and intermetallic separations) can be amended and potentially controlled. The effects of deploying different metal-ligand and backbone subunits, to create bimetallic assemblies with tunable conformational and electronic characteristics, will be examined. Superior catalytic performances will be targeted in the activation and transformation of small molecules and organic substrates. The construction of bimetallic cavities that can mediate appealing and unusual reactivity may be envisaged. Importantly, preliminary results have been acquired (including evidence of bimetallic cooperative mechanism from kinetic studies and DFT calculations), which support the feasibility of the proposed approach and anticipated developments in coupling and polymerization reactions. The underlying aim is to develop novel and cooperative reactivity for these binuclear catalysts in the production of valuable chemicals and polymers from renewable resources. 


Project number9043220
Grant typeGRF
Effective start/end date1/12/21 → …