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Making Xenon a Ligand Using Solid–State Molecular Organometallic Chemistry

Department of Chemistry

About the Project

This PhD position is part of a recently funded project by the Leverhulme Trust. This project between Professor Andrew Weller and Professor Simon Duckett combines organometallic synthesis and characterisation using solid-state molecular organometallic techniques, with analysis using advanced NMR spectroscopic methods.

Andrew Weller’s group has recently pioneered a methodology for the synthesis, characterisation and onward reactivity of highly unstable metal complexes of alkanes (such a pentane and isobutane) under standard laboratory conditions (1). To do this, rather than working in solution (as is normal) we work in single-crystals, isolating reactive metal centres in a “crystalline matrix”. This is similar, in some respect, to the way that the active sites in enzymes operate: the environment that surrounds the metal centre offers stabilisation of high reactive species. We call this solid-state molecular organometallic chemistry (SMOM). In this project, rather than alkanes binding with transition metals, we propose that we can use the same techniques of using organometallic chemistry in the single-crystal to synthesise, isolate and characterise xenon complexes.

While the coordination of xenon perhaps presents a bigger challenge than alkane coordination, we ambitiously propose that the same factors that allow for the stabilisation of alkane complexes in SMOM-chem can be applied to the synthesis and subsequent exploration of reactivity of xenon coordination complexes under routine laboratory conditions. The coordination chemistry of xenon is one of the last frontiers in synthetic chemistry with only a handful of examples reported – all observed under rather extreme conditions. The demonstration of the coordination of xenon to transition metals, and full characterisation using x-ray and NMR techniques, would represent a significant breakthrough in organometallic and coordination chemistry.

In order to do this, the SMOM techniques pioneered by the Weller group, that allow for the observation for xenon coordinating with metal centres using single-crystal to single-crystal reactivity, will be combined with the advanced nuclear magnetic resonance techniques pioneered by Simon Duckett, that probe coordination and mobility of xenon in the crystalline state. Our approach is encouraged by exciting preliminary results in this area from one of our groups (2).

Experimental Approach:
The PhD position will be best suited to an individual who has interests in receiving high-level training in organometallic synthesis, single-crystal x-ray diffraction and advanced NMR spectroscopy. The post will likely be filled by someone who is willing to take on a synthetic challenge, problem-solve in a team environment, and develop their skills by using a wide variety of techniques to resolve structure, bonding and reactivity in organometallic systems. In addition to working with the Weller and Duckett groups, there are further are opportunities to collaborate with the world-leading groups of Professor Stuart Macgregor (Heriot–Watt University, DFT calculations) and the Professor Simon Coles (National Crystallography Service, in situ x-ray studies). The PhD student will work closely with an experienced PDRA on the project, and the precise goals for the studentship can be tailored to reflect the interests of the successful candidate – within the overall objectives of the project.

The demonstration of Xe interacting with metal centres under routine laboratory conditions would represent a significant and fundamental breakthrough in the Chemical Sciences. Capitalising on this would enable an underexplored area of science: the coordination chemistry of the noble gases.

The PhD student will be trained in a range of advanced organometallic/inorganic chemistry techniques, that will allow them to develop, and become expert in, preparing and studying the reactivity of molecular solid-sate organometallic systems. They will become expert in the emergent area of noble gas complexes and receive highly desirable advanced training in NMR spectroscopy and single crystal x-ray diffraction. The PhD student will work jointly with the vibrant and welcoming groups of Weller and Duckett which will help them connect with some of the most exciting challenges faced by inorganic chemistry. All Chemistry research students have access to our innovative Doctoral Training in Chemistry (iDTC): cohort-based training to support the development of scientific, transferable and employability skills: https://www.york.ac.uk/chemistry/postgraduate/idtc/

For more information on the Weller and Duckett groups and research programmes see:
https://www.york.ac.uk/chemistry/staff/academic/t-z/andrew-weller/ and https://www.york.ac.uk/chemistry/staff/academic/d-g/sduckett/

The Department of Chemistry holds an Athena SWAN Gold Award and is committed to supporting equality and diversity for all staff and students. The Department strives to provide a working environment which allows all staff and students to contribute fully, to flourish, and to excel: https://www.york.ac.uk/chemistry/ed/.

Funding Notes

The studentship is available to students who are eligible to pay tuition fees at the UK (home) rate: View Website. It is fully funded for 3 years by the Leverhulme Trust and covers: (i) a tax-free annual stipend at the standard Research Council rate (£15,285 for 2020-21), (ii) tuition fees at the UK rate, (iii) funding for consumables


(1) J. Am. Chem. Soc. 2019, 141, 11700
(2) Angew. Chem. Int. Ed. 2019, 58, 16873.

Candidate selection process:
• You should hold or expect to receive at least an upper second class degree (or equivalent https://www.york.ac.uk/study/international/your-country/) in chemistry or a chemical sciences related subject and be eligible to pay tuition fees at the UK rate
• Applicants should submit a PhD application to the University of York by 11 January 2021
• Supervisors may contact candidates either by email, telephone or web-chat
• Candidates will be notified of the outcome by email

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