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Activating Substrates for Chemical Synthesis with Reactive Aluminium Reagents


   School of Chemical and Physical Sciences

  , Assoc Prof J. Robin Fulton  Applications accepted all year round  Funded PhD Project (Students Worldwide)

Wellington New Zealand Applied Chemistry Inorganic Chemistry Structural Chemistry Synthetic Chemistry

About the Project

Overview A fully funded PhD studentship is available to work with Prof Martyn Coles and A/Prof Robin Fulton at Victoria University of Wellington, New Zealand. The projects involve synthetic inorganic chemistry to develop new chemical reagents based on the recently discovered class of aluminyl anions. Emphasis will be placed on exploring the reactivity of these species with small molecules to convert low value chemical feedstocks to useful building blocks for chemical synthesis.

Background Chemical reagents based on aluminium have traditionally exploited the electron deficiency of this main group metal, which activates substrate molecules by accepting electrons (i.e. Lewis acid). Recent research in our group has isolated a new class of anionic Al(I) compound, referred to as the aluminyl anions [Al(L)] (where L is a dianionic chelating ligand). In contrast to the previously established mode of reactivity, the aluminium centre in these species has an associated lone-pair of electrons and has demonstrated nucleophilic characteristics (i.e. can activate substrates as a Lewis base).

The project will explore the chemical reactivity of these novel compounds for the activation of small molecules. The aim is to understand how these reagents interact with different functional groups, and how this will enable further chemistry to take place at the substrate. Ultimately we will develop compounds that can be used to elaborate readily available chemical feedstocks (e.g. CO2, CO, alkenes etc.) to generate more complex molecules that can be used in chemical synthesis.

The development of bimetallic systems in which the aluminium centre is bonded to another metal M will form a separate component of this work. The synergistic reactivity of the resulting Al–M bonds will also be tested towards the activation and derivatization of small molecules.

Research environment You will work with both Prof Coles and A/Prof Fulton during all aspects of this project. The lab is fully equipped for the synthesis and manipulation of air-sensitive chemicals and reagents, including inert atmosphere gloveboxes and vacuum lines. Analysis of the compounds and reactions will utilize the state-of-the art NMR facility at VUW (including multinuclear NMR, 2-D experiments, variable temperature reaction monitoring) and X-ray diffraction.

The project incorporates an active collaboration with Dr Claire McMullin (University of Bath, UK), who will support the synthetic work with computational analysis of new compounds and reaction pathways.

Requirements A good undergraduate degree (4-year BSc with 1st or 2:1 honours), MSc or postgraduate diploma in Chemistry with experience in synthesis. You must be highly motivated and able to work as part of a team. Full training will be given in all aspects of the project.

Application For further information or to apply please email a cover letter (including the names and contact details of TWO referees) and a current CV to


Funding Notes

The successful candidates will each receive a stipend of $27,500 / year (course and tuition fess are covered).
Applications from international and domestic students are encouraged.

References

1) "Reduction vs. addition: The reaction of an aluminyl anion with 1,3,5,7-cyclooctatetraene" Schwamm, R. J.; Anker, M. D.; Lein, M.; Coles, M. P., Angew. Chem. Int. Ed. 2019, 58, 1489-1493. DOI: 10.1002/anie.201811675.
2) "Isoelectronic Aluminium Analogues of Carbonyl and Dioxirane Moieties" Anker, M. D.; Coles, M. P., Angew. Chem. Int. Ed. 2019, 58, 13452-13455. DOI: 10.1002/ange.201907884.
3) "Aluminium-Mediated Carbon Dioxide Reduction by an Isolated Monoalumoxane Anion" Anker, M. D.; Coles, M. P., Angew. Chem. Int. Ed. 2019, 58, 18261-18265. DOI: 10.1002/anie.201911550.
4) "Carbon–Carbon Bond Forming Reactions Promoted by Aluminyl and Alumoxane Anions: Introducing the Ethenetetraolate Ligand" Anker, M. D.; McMullin, C. L.; Rajabi, N. A.; Coles, M. P., Angew. Chem. Int. Ed. 2020, 59, 12806-12810. DOI: 10.1002/anie.202005301.

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