Topologically Tunable Bimetallic Platforms: Design and Development of Catalytic and Cooperative Reactivity

The bio-inspired development of multimetallic systems displaying cooperative reactivitybetween proximal metal centers has attracted considerable attention. The realization ofcooperative reactivity leading to enhanced catalytic efficiency and selectivity is challengingand often remains elusive. Further investigations and insights are required to elucidate thefactors for attaining and controlling metal-metal cooperativity and synergistic effects betweenactive sites. This proposal is focused on the design, preparation, and application of binuclearassemblies containing cofacial metal-organic subunits that are linked together by an inflexiblebackbone group. Variations in molecular conformation is restricted to axial rotation of thecofacial moieties, but crucially, this permits tuning of intermetallic separations and geometry.By changing the nature of the metal-organic and backbone units, it is envisaged that strategiesto modify and control the relative spatial arrangement and mutual orientation (“topology”) ofthe cofacial metal-organic moieties can be developed, so that the capacity of the resultantframeworks for substrate activation can be probed and adapted. An important goal of thisproposal is the creation of a synergistic and cooperative reaction space between the bimetallicsites. New design approaches are proposed, which can address and resolve issues reported inprevious work as well as afford improved catalytic activity and selectivity, and preliminaryresults are presented as supporting evidence. The underlying aim is to develop attractive andnovel catalytic reactivity for these bimetallic platforms for the production of valuablechemicals from sustainable resources.