Well-defined, bimetallic molecular clefts: A new approach to nitrogen fixation and transformation
Lead Research Organisation:
University of Edinburgh
Department Name: Sch of Chemistry
Abstract
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.
Organisations
People |
ORCID iD |
Jason Love (Principal Investigator) |
Publications
Askarizadeh E
(2010)
Tailoring dicobalt Pacman complexes of Schiff-base calixpyrroles towards dioxygen reduction catalysis.
in Chemical communications (Cambridge, England)
Devoille AM
(2012)
Double-pillared cobalt Pacman complexes: synthesis, structures and oxygen reduction catalysis.
in Dalton transactions (Cambridge, England : 2003)
Givaja G
(2007)
Dioxygen reduction at dicobalt complexes of a Schiff base calixpyrrole ligand.
in Angewandte Chemie (International ed. in English)
Givaja G
(2007)
Design and synthesis of binucleating macrocyclic clefts derived from Schiff-base calixpyrroles.
in Chemistry (Weinheim an der Bergstrasse, Germany)
Volpe M
(2007)
Early transition metal complexes of dinucleating Pacman ligands: X-ray crystal structures of mixed-valence VIII/VIV complexes
in Inorganica Chimica Acta
Volpe M
(2009)
Binuclear cobalt complexes of Schiff-base calixpyrroles and their roles in the catalytic reduction of dioxygen.
in Inorganic chemistry
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 |