The development of new sustainable catalytic systems based on earth abundant metals for fundamentally significant synthetic transformations represents a major objective in modern chemical research at both the academic and industrial level. The drive for increasingly greener and more cost-effective approaches has sparked considerable interest in the replacement of well-established precious metal catalysts (e.g. Ru/Ir/Rh) for base metal catalysts such as those involving iron, nickel, cobalt and manganese.
In the context of a dehydrogenation reaction, the activation of an inert alcohol by an acceptorless strategy makes for an attractive environmentally friendly atom-efficient catalytic process that allows access to a wide range of high-added-value organic products that include aldehydes, acetals, esters, amides, imines and amines . Originally, such acceptorless alcohol dehydrogenation (AAD) routes employed expensive noble metal catalysts to deliver the target organic products, but in recent years the emergence of inexpensive first row transition metal catalysts that can display not only comparable performance but also alternative reactivity patterns has stimulated an upsurge in global interest [2-4]. However, to explore the full potential of such 3d metal dehydrogenation, in terms of substrate/product scope, catalytic activity and temperature stability, there is drive to broaden the library of supporting ligands.
In this PhD project, we develop the concept of remote metal-ligand cooperation to enhance the performance of an AD catalyst. In particular, we will be targeting first row transition metal catalysts that incorporate a proton responsive functionality tethered within their multidentate ligand frame.
Comprehensive screening of their complexes as AD catalysts will be performed with a range of hydrogen rich alcohol substrates to ascertain their relative capacity to generate highly prized products and molecular hydrogen.
This is synthetic chemistry project that will make use of modern approaches to ligand design, metal complexation and catalytic evaluation. The student will gain experience in multiple synthetic techniques including Schlenk-line and glove box techniques. In each stage of the project the student will undergo a comprehensive training programme to allow them to perform the various tasks. The synthetic work will be supported by a wide range of characterisation techniques including 500 and 2 x 400 MHz NMR spectrometers, GC-MS and ESI-MS, single crystal X-ray diffraction, HPLC, GC, and UV/Vis and IR spectrophotometers.
These analytical facilities are supported by dedicated technical staff who can provide training and perform routine measurements as required. In addition, the Synthesis and Catalysis section hold weekly joint group meetings were the student will present their research across multiple disciplines.
Academic entry requirements
UK Bachelor Degree with at least 2:1 in a relevant subject or overseas equivalent.
University of Leicester English language requirements apply (where applicable).
UK/EU applicants only.
When applying, please ensure we have received all of the following required documents by Tuesday 4th February 2020 :
- Application Form
- 2 academic references
- Undergraduate transcripts
If you have completed your undergraduate degree, we will also require your undergraduate degree certificate.
If you have completed a postgraduate degree, we will also require your transcripts and degree certificate.
If we do not have the required documents by the closing date, your application may not be considered for the studentship.
Please refer to guidance at - https://le.ac.uk/study/research-degrees/funded-opportunities/chem-gta-2020
1. G. A. Solan et al., Catal. Sci. Tech., 2017, 7, 1654-1661.
2. S. Schneider et al., Chem. Rev. 2019, 119, 2681-2751.
3. K. Kirchner et al., Acc. Chem. Res., 2018, 51, 1558−1569.
4. R. Kempe et al., Angew. Chem., Int. Ed., 2018, 57, 46–60.