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Photo(redox)-promoted reductive elimination at p-block element centres: new strategies to close ‘transition metal-like’ catalytic cycles

   Department of Chemistry

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  Dr Daniel Scott  No more applications being accepted  Competition Funded PhD Project (UK Students Only)

About the Project

The University of Bath is inviting applications for the following PhD project commencing in October 2023.

Overview of the Research:

The development of homogeneous catalysis using well-defined transition metal (TM) complexes was a triumph of 20th century chemical research that revolutionised the field of synthetic chemistry. Unfortunately, this achievement was also heavily dependent on the use of precious metal catalysts (indeed, in this context, ‘TM catalysis’ and ‘precious metal catalysis’ are often all but synonymous). These metals suffer from major issues of scarcity, expense, and in many cases toxicity, which renders them unattractive for use in many contexts.

As a result, the 21st century has seen increasingly concerted efforts to achieve the same chemical transformations using alternative catalysts based on more benign, earth-abundant elements. This has led to particular interest in p-block element complexes that possess unusual oxidation states, electronic configurations and/or coordination geometries, which lead to ‘unsaturated’ electronic structures with small HOMO-LUMO gaps, similar to those of catalytically-active transition metals.

Many such complexes have now been isolated and, indeed, much of their stoichiometric reactivity, such as oxidative addition (OA), closely mirrors that of TMs. However, attempts to develop TM-like catalytic reactions have almost all been unsuccessful. This is largely due to difficulties in achieving TM-like reductive elimination (RE) steps, which are a common feature required of such catalytic reactions.

To overcome this problem, this project will study the use of light to drive reductive elimination reactions at p-block element centres. Two strategies will be investigated. In the first, direct photoexcitation of high-valent p-block complexes will induce RE via photoinduced electron transfer from the ligands to the p-block element centre. In the second, a photo- and redox-active (photoredox) catalyst will be used to effect transient oxidation of the p-block complex, which will similarly promote RE.

Project keywords: inorganic chemistry, main group chemistry, photochemistry, catalysis. 

Candidate Requirements:

Applicants should hold, or expect to receive, a First Class or good Upper Second Class Honours degree (or the equivalent). A master’s level qualification would also be advantageous.

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

Enquiries and Applications:

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

Formal applications should be submitted via the University of Bath’s online application form for a PhD in Chemistry prior to the application deadline of Sunday 22 January 2023.

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

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.

Exceptional Overseas students (e.g. with a UK Master’s Distinction or international equivalent and relevant research experience), who are interested in this project, should contact the lead supervisor in the first instance to discuss the possibility of applying for supplementary funding.

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, a stipend (£17,668 per annum, 2022/23 rate) and research/training expenses (£1,000 per annum) for up to 3.5 years. Eligibility criteria apply – see Funding Eligibility section above.

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