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| New hydrophobic iron based oxidation catalysts for selective methane oxidation | ||||||||||||||||||
Methane is the major constituent of natural gas and as such will become a highly valuable carbon feedstock as crude oil supplies dwindle. It is also a major contributor to greenhouse gas warming. Thus it is crucial that we find new and improved ways of trapping and utilising methane. This project is involved with the design of a family of novel hydrophobic high valent iron oxygenation catalysts based on polypyridine chelate ligands for the direct exothermic selective oxidation of methane to methanol. We aim to secure the first ambient temperature catalyst for direct methane oxidation to methanol rivalling industrial steam reforming. The considerable challenges (its chemical inertness) will be overcome through concentration and then activation of the methane C-H bond (via C-H abstraction) in proximity to a reactive high valent iron-bound O radical contained within a hydrophobic supramolecular cavity. The hydrophobic topology of the cavity will be designed to favour methane rather than methanol coordination so as to suppress over oxidation and increase the selectivity towards methanol as product. The ligands surrounding the active iron centre will be designed to facilitate the formation of a highly reactive perferryl iron(V)oxo oxygenating centre. This project is the first of its kind to incorporate a powerful iron-based oxygenating centre within a molecular superstructure possessing a high methane affinity. 1. Guisado-Barrios, G.; Li, Y, Slawin, A.M.Z.; Richens, D.T.; Gass, I.A.; Murray, P.R.; Yellowlees, L.J.; Brechin, E.K. ‘High Spin d5 Complexes of Tris(6-hydroxymethyl-2-pyridylmethyl)amine (H3L): Hepta-coordinated [Mn(H3L)]Cl2 and [Fe3L2](ClO4)3; an Unusual Weakly Antiferromagnetically-Coupled Alkoxide-Bridged Linear Triiron(III) Complex with a Tight Fe-O-Fe Angle’. Dalton Trans., (2008), 551–558. 2. Richens D.T.; Jain, S.L.; Gale, A.C., ‘Kinetics of the reaction of mer-tris(picolinato) iron(III) with hydrogen peroxide in pyridine: role of hydroxyl radicals in subsequent catalytic oxygenation of cyclohexane to the ketone’, Inorg. React. Mech. (2007), 6(3) 169-183. 3. Marr, S. B.; Carvel, R.O.; Richens, D.T.; Lee, H-J.; Lane, M.; Stavropoulos, P., 'A Comparison Between Iron and Ruthenium Complexes Mediating GifIV-type Oxygenations on Cyclohexane', Inorg. Chem., (2000), 39, 4630-4638. |
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Research Assessment Exercise (RAE) 2008 Results
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