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Mechanisms and Kinetics of ‘Frustrated Lewis Pair’ Hydrogenation

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  • Full or part time
    Dr Fuchter
    Dr Tighe
  • Application Deadline
    Applications accepted all year round

Project Description

Applications are sought for a 3-year studentship in metal-free hydrogenation catalysis. The successful candidate will be supervised by Dr Matthew Fuchter and Dr Andrew Ashley at the Department of Chemistry, and Dr Chris Tighe at the Department of Chemical Engineering, Imperial College London, starting October 2016. This project is kindly supported by GlaxoSmithKline, through PharmaCat, a collaboration between ICL and the chemical industries.

Project: Catalytic hydrogenation reactions, which are of immense importance throughout the chemical sciences (from bulk chemical to pharmaceutical synthesis), are largely dependent on the use of rare, expensive, and often toxic precious metal catalysts (e.g. Ru, Rh, Pd, Pt). There is a huge drive to develop cheaper and more benign alternatives. In recent years substantial progress has been made with ‘frustrated Lewis pair’ (FLP) catalysts, which consist of a sterically bulky Lewis acid and base, which are precluded from forming stable adducts. These systems, typically based on innocuous, inexpensive main group elements, are capable of heterolytically cleaving H2 into formal H+/H- fragments, which can then be transferred to a variety of reducible substrates. Rapid advances in the past six years (by our groups and others) have seen the scope of this methodology expand from simple imines and aziridines to N-heteroaromatics, alkenes and carbonyls, among many other substrates.
Because of the speed with which this area has developed, many important aspects of FLP-catalysed hydrogenation chemistry have received limited attention; for example, there has been very little direct experimental investigation into reaction mechanisms and kinetics, leading to uncertainty in, for example, the nature of the rate-determining step. For more complex FLP reactions such as carbonyl hydrogenations, even less experimental information is available, leading to much greater uncertainty. Importantly, knowledge of reaction and catalyst deactivation/inhibition mechanisms is fundamental to reactor and process design and scale-up, as well as for designing more effective catalysts. Measurements of intrinsic kinetics can be difficult to achieve; often, it is necessary to develop apparatus and techniques tailored to a specific reaction scheme, to ensure that mass transfer does not control the measured rates.

This research project will investigate FLP catalysed hydrogenations, measuring intrinsic reaction rates and the evolution of reaction intermediates and products in-situ. From these studies, the qualitative reaction mechanism, together with transient measurements of reactant and product concentrations, may be combined with a mathematical framework to extract kinetics of individual reaction pathways. This information will be used to optimise the catalyst structure.

Eligibility and Funding The position would suit an ambitious, highly motivated and practical researcher with interests in industrial organic and main group inorganic chemistry and catalysis, coupled with strong mathematical skills. Relevant previous research experience in academic laboratories essential. Funding is available to students with UK residency status and will cover tuition fees and provide a tax-free stipend, including a London allowance. Applicants should hold (or expect to be awarded) a First Class Masters degree (i.e. MSci, or MChem) in Chemistry.
How to Apply: Interested candidates are encouraged to make informal contact A.S.A.P. with Dr Fuchter ([email protected]), Dr Ashley ([email protected]), or Dr Tighe ([email protected]), attaching a CV.

Formal applications should be made through the Imperial College online application process, which can be accessed here. Please make reference to the above project title in the Proposed Research Topic field. Short-listed candidates will be required to attend an interview in person at Imperial College London, which will be held as soon as possible.

Funding Notes

1. Scott D. J., Fuchter M. J., Ashley A. E.*, Non-Metal Catalysed Hydrogenation of Carbonyl Compounds Journal of the American Chemical Society, 2014, 136, 15813-15816; highlighted in C&EN.
2. Scott D. J., Fuchter M. J., Ashley A. E.*, Metal-free Hydrogenation Catalyzed by an Air-stable Borane: Use of Solvent as a Frustrated Lewis Base Angewandte Chemie - International Edition, 2014, 53, 10218-10222; HOT PAPER.
3. Scott D. J.,

Simmons, T.R., Lawrence, E.J., Wildgoose, G.G., Fuchter M. J., Ashley A. E.*, Facile Protocol for WaterTolerant “Frustrated Lewis Pair”-Catalyzed Hydrogenation ACS Catalysis, 2015, 5, 5540–5544.

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