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PhD studentship in Main Group Synthesis and Catalysis


   School of Chemistry

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  Dr P Kilian  Applications accepted all year round  Competition Funded PhD Project (Students Worldwide)

About the Project

Research activities in Kilian group are centred on the design and synthesis of novel organophosphorus and heavier Group 15 (As, Sb, Bi) organoelement compounds. We synthesize new compounds for various practical applications, such as spin labels, or catalysis. 

Our research has recently been directed towards new coupling reactions. In coupling reactions two species are linked together with the elimination of a small molecule. In the field of main group chemistry, dehydrocoupling reactions (E−H + H−E’ → E−E’ + H2, E = main group element) have provided an alternative to traditional reductive strategies for the formation of E−E bonds. These reactions have been invaluable not only in inorganic synthesis but also in polymer formation, transfer hydrogenation, and hydrogen storage. Coupling reactions are typically catalysed by transition metals. This has several drawbacks; many of the metals used are nonabundant and thus expensive, which limits their sustainability and economy. Often, the metals are toxic, which leads to problems when these catalysts are used in the synthesis of pharmaceuticals. As such, the replacement of transition metals with cheaper and more readily available main group reagents is a tantalizing prospect.

Recently we expanded the range of coupling reactions by a series of highly unusual ‘dealkacouplings’, in which a direct E−E bond is formed with concomitant elimination of a C−H coupled product, alkane.

Funding is available to further expand this concept to develop new carbon-element coupling reactions. To achieve this aim, we will utilise cooperativity of two main-group centres placed in close proximity on a clamping molecular framework. This will mitigate the need for transition metal based catalysts in our transformations. The project will involve synthetic work under inert atmosphere, multinuclear NMR and single crystal X-ray diffraction. Mechanistic studies supported by computations (in collaboration with computational chemists) will also be integral part of the project.

Students interested in undertaking a PhD in the Kilian group in this research area should register their interest as soon as possible. Informal enquiries can be made to Dr Kilian ([Email Address Removed]). For more information see the group web pages at http://kiliangroup.wp.st-andrews.ac.uk/

Please see: http://www.st-andrews.ac.uk/chemistry/prospective/pg/ for the application procedure or e-mail [Email Address Removed] for more information regarding PhD opportunities at St Andrews. We encourage applications for the EPSRC CDT in Critical Resource Catalysis (https://www.criticat.co.uk/).Note the next closing date for applications is 14 January 2022.


Funding Notes

Please see: https://www.st-andrews.ac.uk/chemistry/prospective/pgr/ for the application procedure or e-mail [Email Address Removed] for more information regarding PhD opportunities at St Andrews. We encourage applications for the EaSiCAT Centre for Doctoral training (https://www.criticat.co.uk/) and from Chinese nationals through the St Andrews CSC Scheme (https://csc.wp.st-andrews.ac.uk/). There are opportunities for self-funded PhD students to make use of the St Andrews Handsel Scheme to fund the difference between home and international fees.

References

P. S. Nejman, T. E. Curzon, M. Bühl, D. McKay, J. D. Woollins, S. E. Ashbrook, D. B. Cordes, A. M. Z. Slawin and P. Kilian*
Phosphorus-Bismuth Peri-Substituted Acenaphthenes: A Synthetic, Structural, and Computational Study
Inorg. Chem. 2020, 59, 5616–5625
DOI: 10.1021/acs.inorgchem.0c00317
L. J. Taylor, M. Buühl, B. A. Chalmers, M. J. Ray, P. Wawrzyniak, J. C. Walton, D. B. Cordes, A. M. Z. Slawin, J. D. Woollins, and P. Kilian*
Dealkanative Main Group Couplings across the peri-Gap
J. Am. Chem. Soc. 2017, 139, 18545-18551
DOI: 10.1021/jacs.7b08682

L. J. Taylor, B. A. Surgenor, P. Wawrzyniak, M. J. Ray, D. B. Cordes, A. M. Z. Slawin and P. Kilian*
Spontaneous Dehydrocoupling in Peri-Substituted Phosphine-Borane Adducts
Dalton Trans. 2016, 45, 1976 – 1986 (invited contribution to themed issue “Phosphorus Chemistry: Discoveries and Advances”)
DOI: 10.1039/C5DT02539G OPEN ACCESS

B. A. Chalmers, M. Bühl, K. S. Athukorala Arachchige, A. M. Z. Slawin, P. Kilian*
Geometrically Enforced Donor-Facilitated De-hydrocoupling Leading to an Isolable Arsanylidine-Phosphorane
J. Am. Chem. Soc. 2014, 136, 6247–6250 (communication).
DOI: 10.1021/ja502625z OPEN ACCESS

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