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Catalytic Applications of Electronically-Perturbed Pnictogens

  • Full or part time

    Prof Michael Whittlesey
  • Application Deadline
    Sunday, December 08, 2019
  • Competition Funded PhD Project (European/UK Students Only)
    Competition Funded PhD Project (European/UK Students Only)

Project Description

The University of Bath is inviting applications for the following PhD opportunity based in the Department of Chemistry.

The heavier pnictogens are attractive elements for investigation as catalytic centres. Unlike much of the main group, these species show readily accessible redox chemistry and umpolung behaviour. Furthermore, they are amenable to electronic perturbation via the judicious selection of ligands. This is supported by their highly covalent bonding and confinement to the III/IV redox couple which allows bidentate ligands to support systems with residual reactive substituents.

N-heterocyclicphosphanes (NHPs) are one such class electronically perturbed group 15 species, which share structural motifs with the hugely successful N-heterocyclic carbene frame work. Charge-separated NHPs have recently gained prominence in catalytic transformations. P-hydrido-1,3,2-diazaphospholenes (NHP-H) show significant π-delocalisation leading to an increased charge density at the phosphorus-bound hydrogen atom conferring upon it hydridic character. This remarkable “umpolung” character has been exploited in catalytic transformations wherein these NHP-H species act as “molecular hydrides” and, as a consequence of their unique electronics, have been measured to have some of the highest hydridicities hereto reported. These compounds have been disclosed as excellent catalysts for reduction of organic substrates however expansion beyond hydride substituents has been less well investigated. Furthermore, such compounds share many attributes with main group metal hydrides which have been used in catalytic dehydrocoupling, a reaction unexplored for NHPs.

Dehydrocoupling has recently emerged as the pre-eminent selective method to generate E-E` bonds in the p-block via the coupling of a hydridic and protic substrate to yield a new heteroelement bond and dihydrogen. Reported catalysts for this transformation are principally electrophilic metal centers wherein the hydridic nature of the M-H bond results in sufficient basicity to deprotonate the protic coupling partner to generate a new M-X bond and dihydrogen. Thus, this project will focus on the exploration of N-heterocyclicphosphanes and their analogues in a number of catalytic applications. These include the reduction of main group centres, the heterodehydrocoupling of p-block hydride and proton sources and the catalytic synthesis of inorganic polymers and materials. Finally, NHPs have the potential to perform as excellent radical initiators and the exploration of hitherto unreported NHP-X species which may access the single-electron manifold will feature in the project.

Candidate requirements:

Applicants should hold, or expect to receive, a First Class or Upper Second Class UK Honours degree (or the equivalent qualification gained outside the UK) in a relevant subject. Experience in a synthetic inorganic or organometallic laboratory is highly desirable. Non-UK applicants must meet our English language entry requirement

How to apply:

Informal enquiries are welcomed and should be addressed to Dr David Liptrot.

Formal applications should be made via the University of Bath’s online application form for a PhD in Chemistry:

Please ensure that you quote the supervisor’s name and project title in the ‘Your research interests’ section.

More information about applying for a PhD at Bath may be found here:

Anticipated start date: 28 September 2020.

Funding Notes

UK and EU candidates applying for this project will be considered for a University Research Studentship which will cover UK/EU tuition fees, a training support grant of £1,000 per annum and a tax-free maintenance allowance at the UKRI Doctoral Stipend rate (£15,009 in 2019-20) for a period of up to 3.5 years.

How good is research at University of Bath in Chemistry?

FTE Category A staff submitted: 33.10

Research output data provided by the Research Excellence Framework (REF)

Click here to see the results for all UK universities

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