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Masked Phosphenium Ions to Break New Ground in Synthesis and Catalysis


   Department of Chemistry

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  Dr Ruth Webster  No more applications being accepted  Funded PhD Project (UK Students Only)

About the Project

The University of Bath is inviting applications for the following funded PhD project commencing in October 2022.

The PhD student will work in the area of main group catalysis, covering synthetic methodology and the investigation of reaction mechanisms.

The chemistry of divalent phosphenium ions, R2P+, is elusive. Stable examples are scarce and usually require heteroatom substituents, RE (E = N or O). However, this stability deactivates the P centre towards reactivity. As a result, applications of (RE)2P+ ions are rare. Controlled access to unstabilised phosphenium ions has only recently been disclosed in our recent work in ACS Catalysis. Through a combination of experimental and computational studies we discovered a new route to exploit unstabilised phosphenium ions in catalysis, employing them in the hydrosilylation of carbonyl compounds.

The project focuses on the reactivity of unstabilised phosphenium ions and will probe structure/stability relationships along with onward catalysis studies, for example the reactivity of multiply bonded species, small molecule activation and umpolung chemistry.

The project will involve a close collaboration between our group in Bath and the group of Professor Stuart Macgregor at Heriot Watt University (subject to contract), where DFT studies will feed in to our synthetic chemistry investigations (and vice versa). Applicants should have an interest in catalysis and reaction mechanisms. A background in air-sensitive chemistry is not essential as training will be provided.

Project keywords: Organocatalysis, main group chemistry, homogeneous catalysis, reaction mechanisms.

Candidate Requirements:

Applicants should hold, or expect to receive, a First Class or good Upper Second Class Honours MChem or MSci degree (or the equivalent) or a BSc degree (or the equivalent) with industrial training experience.

Non-UK applicants must meet our English language entry requirement.

Enquiries and Applications:

Informal enquiries are welcomed and should be directed to Dr Ruth Webster on email address [Email Address Removed].

Formal applications should be made via the University of Bath’s online application form for a PhD in Chemistry (full-time).

More information about applying for a PhD at Bath may be found on our website.

Interviews will take place on w/c 8 August 2022.

Funding Eligibility:

To be eligible for funding, you must qualify as a Home student. The eligibility criteria for Home fee status are detailed and too complex to be summarised here in full; however, as a general guide, the following applicants will normally qualify subject to meeting residency requirements: UK and Irish nationals (living in the UK or EEA/Switzerland), those with Indefinite Leave to Remain and EU nationals with pre-settled or settled status in the UK under the EU Settlement Scheme. This is not intended to be an exhaustive list. Additional information may be found on our fee status guidance webpage, on the GOV.UK website and on the UKCISA website.

Equality, Diversity and Inclusion:

We value a diverse research environment and aim to be an inclusive university, where difference is celebrated and respected. We welcome and encourage applications from under-represented groups.

If you have circumstances that you feel we should be aware of that have affected your educational attainment, then please feel free to tell us about it in your application form. The best way to do this is a short paragraph at the end of your personal statement.


Funding Notes

A studentship includes Home tuition fees and a stipend at the UKRI rate (£16,062 per annum, 2022/23 rate) for up to 3.5 years. The successful student will also have access to funds to support research expenses, training and travel. Eligibility criteria apply – see Funding Eligibility section above.

References

This PhD builds upon our preliminary publication in this field: Phosphirenium Ions as Masked Phosphenium Catalysts: Mechanistic Evaluation and Application in Synthesis, ACS Catal. 2021, 11, 5452–5462.

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