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Molecular s-block assemblies for Redox-active bond activation and catalysis: repurposing the s-block as 3d-elements

   Department of Chemistry

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  Prof Michael Hill  No more applications being accepted  Competition Funded PhD Project (Students Worldwide)

About the Project

The University of Bath is inviting applications for the following PhD project commencing in October 2022 under the supervision of Professor Michael Hill in the Department of Chemistry.

Eligible applicants will be considered for a fully-funded studentship – for more information, see the Funding Notes section below.

Overview of the Project:

This project builds on our recent report (J. Am. Chem. Soc. 2021, 143, 17851) that a heterobimetallic assembly comprising a low oxidation state Mg-Mg bonded unit and two sodium cations is readily accessible by reduction of a conventional molecular Mg(II) bis-anilide. The electronic structure and chemistry of the {Mg2Na2} assembly is dependent not only on the presence of the formally Mg(I) centres but also on the cooperative interaction of the Mg-Mg bond with the sodium cations.

During this project, you will extend this general design principle to access a family of formally low oxidation state group 1 / group 2 heterobimetallics, including unprecedented examples of metal-metal bonded species containing the heavier group 2 elements, Ca, Sr and Ba. The metal-metal bonded interactions of the resultant compounds will possess narrow and manipulable frontier orbital energies and provide unprecedented access to earth-abundant s-block systems that display potentially reversible redox behaviour. The reductive reactivity of the compounds will, thus, be assessed toward small molecules such as H2, CO, CO2 and N2. Their potential redox activity may also allow the construction of catalytic manifolds, which display a higher degree of commonality with those derived from the nd orbital configurations of transition metals than those of isolated group 1 and 2 centres. Although the project will provide training in the synthesis (Schlenk line and glovebox techniques) and analysis (X-ray diffraction, multinuclear NMR) of air- and moisture-sensitive compounds, there will also be opportunities to perform quantum chemical calculations.

Project keywords: air-sensitive main group chemistry; low oxidation state; s-block; small molecule activation; catalysis.

Candidate Requirements:

Applicants should hold, or expect to receive, a First Class or good Upper Second Class Honours degree (or the equivalent) in Chemistry and possess an interest in main group and inorganic chemistry and catalysis, preferably with some prior experience of air- and moisture-sensitive . 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 Professor Michael Hill (email: [Email Address Removed]).

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

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

Candidates applying for this project may be considered for a 3.5-year Engineering and Physical Sciences Research Council (EPSRC DTP) studentship. Funding covers tuition fees, a stipend (£15,609 per annum, 2021/22 rate) and research/training expenses (£1,000 per annum). EPSRC DTP studentships are open to both Home and International students; however, in line with guidance from UK Research and Innovation (UKRI), the number of awards available to International candidates will be limited to 30% of the total.


For an overview of group 2 catalysis in the Hill group: Chem. Soc. Rev. 2016, 45, 972
Direct background to the project: J. Am. Chem. Soc. 2021, 143, 17851 and references therein.
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