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Biomimetic metal complexes: reactivity and reaction mechanisms (WRIGHTJU16SF)

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  • Full or part time
    Dr Wright
  • Application Deadline
    No more applications being accepted
  • Self-Funded PhD Students Only
    Self-Funded PhD Students Only

Project Description

New methods to reduce and manage our energy needs are vital. Enzyme catalyse a variety of reaction important processes in this area, for example the interconversion of hydrogen and protons, carbon dioxide activation and nitrogen fixation. Exploiting the potential of the natural catalysts requires a deep understanding of the chemistry involved and how to reproduce it in small molecule mimics. In our group, we are tackling this challenge using a combination of synthetic organometallic chemistry and specialised mechanistic techniques. Active areas of interest include:

i) Development of di-iron complexes inspired by the [FeFe]-hydrogenase for the activation of dihydrogen. The enzyme system is extremely efficient in interconversion of dihydrogen with protons and electrons, but as yet artificial {2Fe2S} models cannot match this. By understanding how these molecules react with protons and electrons we are beginning to unravel how to make more efficient and robust catalysts.
ii) Nitrogen fixation using mononuclear iron and molybdenum complexes. Nitrogen fixation is an energy-intensive process because of the kinetic barrier to reaction of dinitrogen and dihydrogen. Catalysis can lower this barrier: here we will tackle this challenge using well-defined mononuclear metal complexes.
iii) Carbon dioxide fixation using molybdenum-dithiolenes. Turning carbon dioxide into useful materials is a challenging process: it is a kinetically inert molecule that is difficult to activate. Nature can do that to give a molecule called formate: a potential fuel. Our work in this area is focussed on mimicking the vitally-important enzyme groups as part of the organometallic framework.

All of these areas for a PhD studentship are excellent opportunities to develop skills across synthetic chemistry and to gain experience in advanced physical methods such as stopped-flow IR and UV spectroscopy (ref. i) and spectroelectrochemistry (ref. iii, iv) with support from computational simulation. Informal enquiries can be made to Dr Joseph Wright.

Funding Notes

This PhD project is offered on a self-funding basis. It is open to applicants with funding or those applying to funding sources. Details of tuition fees can be found at http://www.uea.ac.uk/pgresearch/pgrfees.

A bench fee is also payable on top of the tuition fee to cover specialist equipment or laboratory costs required for the research. The amount charged annually will vary considerably depending on the nature of the project and applicants should contact the primary supervisor for further information about the fee associated with the project.

References

i) Wright and Pickett, Chem. Commun., 2009, 45, 5719–5721
ii) Turrell et al., Angew. Chem. Int. Ed., 2010, 49, 7508–7511
iii) Jablonskytė et al., J. Am. Chem. Soc., 2011, 133, 18606–18609
iv) Webster et al., Chem.—Eur. J., 2012, 18, 11798–11803

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