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Nitrogen activation by first-row transition metals (WRIGHTJU19SF)

  • Full or part time
  • Application Deadline
    Friday, May 31, 2019
  • Self-Funded PhD Students Only
    Self-Funded PhD Students Only

Project Description

Nitrogen fixation is essential in supporting modern societies: food production for a growing global population is dependent on our ability to produce fertilizers on a grand scale. The Harber process has been used for this for well over 100 years but is extremely energy-intensive. Finding alternative, low-energy, approaches to nitrogen fixation is thus a key part of cutting global energy usage.

Microbes can fix nitrogen under benign conditions using enzymes based on iron and molybdenum centres. These elegant catalysts use organometallic cores at their centres. Mimicking this chemistry in small molecules is both vitally important for society and a Grand Challenge in driving our understanding of this fascinating chemistry.

In this PhD project, we will tackle this challenge using a combination of synthetic organometallic chemistry and specialised mechanistic techniques. The use of secondary interactions is now well-established in nitrogen fixation,i and this project will focus on developing new ligand architectures to create novel mononuclear iron and molybdenum systems which can activate dinitrogen at low overpotentials. A key starting point will be the combination of our existing expertise in iron chemistry,ii,iii in combination with advanced spectroscopiesiv to deepen our understanding of the reactivity of these systems.

The project involves synthesis of mononuclear dinitrogen complexes, their characterisation by X-ray crystallography and a range of spectroscopic techniques, and study of their reactivity using stopped-flow and electrochemical techniques. Thus, it will provide a very broad-based training in inorganic synthesis, molecular characterisation and physical measurement, in the excellent facilities of the interdisciplinary Energy Materials Laboratory.

A start date prior to October 2019 is possible, but should be discussed with the supervisor in the first instance

More information:
Type of programme: PhD
Mode of study: Full-time
Start date of the project: October 2019 
For more information on the supervisor for this project, please visit:

Entry Requirements:
Acceptable first degree: Chemistry (The standard minimum entry requirement is 2:1).

Please note: Applications are processed as soon as they are received and the project may be filled before the closing date, so early application is advisable.

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 View Website.

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.


i) Creutz, S. E. & Peters, J. C. Exploring secondary-sphere interactions in Fe-NxHy complexes relevant to N2 fixation, Chem. Sci., 2017, 8, 2321

ii) Danopoulos, A. A.; Wright, J. A. & Motherwell, W. B., Molecular N2 complexes of iron stabilised by N-heterocyclic 'pincer' dicarbene ligands, Chem. Commun., 2005, 41, 784.

iii) Turrell, P. J.; Wright, J. A.; Peck, J. N. T.; Oganesyan, V. S. & Pickett, C. J. The Third Hydrogenase: A Ferracyclic Carbamoyl with Close Structural Analogy to the Active Site of Hmd, Angew. Chem. Int. Ed., 2010, 49, 7508

iv) Jablonskytė, A.; Wright, J. A.; Fairhurst, S. A.; Webster, L. R. & Pickett, C. J. [FeFe] Hydrogenase: Protonation of {2Fe3S} Systems and Formation of Super-reduced Hydride States, Angew. Chem. Int. Ed., 2014, 53, 10143

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