PhD Studentship - Actinide-Element Multiple Bonds for Covalency Quantification and Catalysis

Research theme: Environmental Degradation of Materials

How to apply: uom.link/pgr-apply-2425

Funding for this project covers tuition fees, UKRI minimum annual stipend (currently £20,780/annum) and up to a £5k/annum research training support grant for the full duration of the 4-year programme.

Metal-ligand multiple bonding is a burgeoning area for making chemically novel structural motifs, probing chemical bonding, and being applied to catalysis, some of which defines the state-of-the-art in element-element bond forming reactions. Most metal-ligand multiple bonds involve transition metals, but in recent years we have advanced actinide-ligand multiple bonding by realising unprecedented bonding combinations (e.g. Nat. Chem. 2024, 16, 780; J. Am. Chem. Soc. 2024, 146, 4098; Nat. Chem. 2022, 14, 342; J. Am. Chem. Soc. 2022, 144, 9764), quantifying the chemical bonding by NMR spectroscopy (e.g. Chem. Sci. 2024, 15, 238; J. Am. Chem. Soc. 2023, 145, 21766; Nat. Commun. 2021, 12, 5649; J. Am. Chem. Soc. 2021, 143, 9813), and developing their reactivity (e.g. Nat. Commun. 2020, 11, 337). Nevertheless, there are still many elusive actinide-ligand multiple bonds that would be ground-breaking to secure, and much to do probing the chemical bonding and developing realistic catalytic cycles in order to develop a full understanding of structure-bonding-reactivity relationships for the actinides. To address the aforementioned challenges, this Bicentenary PhD Scholarship will: (i) Extend our range of actinide-ligand multiple bonds, using prior group 14-16 linkages as a springboard, where in particular we target high-value actinide-group14/15 multiple bonds; (ii) rigorously probe the actinide-element multiple bonds with a range of characterisation techniques, where in particular we will quantify the chemical bonding using solution and solid-state NMR spectroscopy underpinned by chemical shift anisotropy calculations; (iii) target stoichiometric then catalytic reactivities, for example metathesis and group 14/15-element bond formation. In addition to the wide range of transferable skills developed during a PhD, the appointed researcher will learn and use: (i) Schlenk and glove box techniques; (ii) characterisation methods, e.g. crystallography, NMR, IR, Raman, UV/Vis/NIR, and EPR spectroscopies, magnetometry, and quantum chemical calculations; (iii) reactivity studies supported by analytical characterisation and modelling methods.

Applicants should have, or expect to achieve, at least a 2.1 honours degree or a master’s (or international equivalent) in a relevant science or engineering related discipline.

To apply, please contact the main supervisor; Prof Steve Liddle - steve.liddle@manchester.ac.uk. Please include details of your current level of study, academic background and any relevant experience and include a paragraph about your motivation to study this PhD project.

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