Well-defined, bimetallic molecular clefts: A new approach to nitrogen fixation and transformation

Lead Research Organisation: University of Edinburgh
Department Name: Sch of Chemistry


A new macrocyclic scaffold has been developed that will assist in the construction of innovative bimetallic molecules where both the immediate environment and juxtaposition of the metals are defined by design. The hinged, or Pacman topology that these compounds adopt will help promote scientifically unique and potentially commercially exploitable chemistry of nitrogen by providing a well-defined and easily-studied reaction pocket. Initially, the preparation and characterisation of new, low valent, early transition metal (titanium, zirconium, vanadium, lanthanides) Pacman compounds for dinitrogen transformation will be considered. This is an original, prefabricated dinuclear approach to dinitrogen activation and will yield nonfragmentary compounds that are primed to react with organic substrates to form new N-E bonds (E = H, C, Si). The reactivity of these novel compounds will be controlled by judicious choice of metal and reasoned modification of the ligand periphery. Hydrogenation, silylation, cycloaddition and N-atom transfer reactions will be evaluated as stoichiometric and catalytic routes to the incorporation of dinitrogen-derived N into organic substrates.


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Description We initiated research into dinuclear metal compounds that adopt 'Pacman'-like structures. The reactivity within the bimetallic molecular cleft (Pacman mouth) was expected to be different to that outside, and was hoped that reactions towards the reduction of dinitrogen could be achieved. While the reduction of dinitrogen was not observed, we found that cobalt complexes were able to catalyse the reduction of dioxygen to water, a reaction that is important in fuel cell operation and so very relevant to current scientific and societal challenges.
Exploitation Route Our work has been cited by others in the area, in particular by those investigating alternatives to Pt catalysts for fuel cells
Sectors Chemicals,Energy