Shape-Persistent Binuclear Complexes Supported by Chelating C-Donor Ligands: Polymerization Catalysis and Bimetallic Cooperativity

Project: Research

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The development of novel polymeric materials with desirable physical and chemical properties, and new and efficient methods for their production, are attractive endeavors that can reduce waste. In bimetallic cooperativity, the adjacent or proximal active sites react in acomplementary and synergistic manner to achieve superior activity and selectivity. Interest in multimetallic catalysts are inspired by their prevalence as metalloenzymes, but studies are needed to provide further insights into achieving and harnessing cooperative reactivity. In this proposal, a modular approach will be employed in the design and synthesis of shape-persistent binuclear complexes linked by a rigid component, with predefined to adjustable metal···metal distances (and no metal–metal bonding). For the latter, conformational changes are effectively limited to axial rotation within the bis(metal-organic) moiety, yet such rotations allowvariations in intermetallic distances and mutual orientation of coordination sites. The impact of combining diverse metal-organic and linker subunits, to produce bimetallic frameworks with tunable spatial arrangement of metal-organic fragments and intermetallic geometry, will be addressed. Novel strategies that can increase catalytic efficiencies and modify reactivity and selectivity are proposed, and preliminary results in support of these have been obtained. The underlying objectives are to probe the structural factors that engender cooperative effects, examine their influence upon polymerization behavior, and develop novel catalysts for theproduction of polymers with appealing and unusual composition and properties. It is envisaged that binuclear catalysts displaying synergistic and cooperative reactivity can be created.


Project number9043050
Grant typeGRF
Effective start/end date1/01/21 → …