About the Project
Expressions of interest are invited for a CSC-funded PhD studentship to work on homogeneous catalysis under the supervision of Dr Xacobe Cambeiro at Queen Mary University of London (QMUL).
PROJECT. The main objective of this research project is to develop new and sustainable methods for the reduction of alkenes and alkynes combining bioinspired Fe-based catalysts, photocatalysts and visible light as a source of energy.
Catalytic hydrogenation and related hydrofunctionalisation of alkenes and alkynes are among the most relevant transformations in chemical industry in terms of scale, and they are vital for a number of industries. However, these methods find important challenges in terms of sustainability, namely: (i) They make extensive use of precious metal catalysts, such as Pt, Rh or Ir, and (ii) To be thermodynamically favoured, they require the use of strong reductants such as H2 or reduced metals. Methods for catalytic hydrogenation using Earth-abundant metals such as Fe aim at addressing challenge (i). In our group, with the use of photocatalysis, we aim to capture the energy of light to promote such reactions with mild, clean reductants such as amines or ideally¬¬ water, which would be otherwise unreactive
The successful applicant will work towards this objective by studying the reactivity or organometallic Fe complexes –including Fe hydrides and alkyl-Fe compounds– against organic substrates, as well as developing new methods for the light-driven generation of these important Fe intermediates. The project will require the evidence-based design of complex multimetallic catalytic cycles, using a wide range of methods and instruments for mechanistic investigation.
LEARNING. The student will receive training in organic synthesis and organometallic chemistry, including advanced experimental and computational techniques for the investigation of reaction mechanisms. Laboratory techniques will include standard organic and organometallic synthesis, Schlenk techniques for working under inert atmosphere, as well as photochemistry. In addition, the applicant will have the opportunity to acquire relevant transferable skills, such as oral and written presentation of research results and supervision of less experienced researchers. QMUL has free language courses available for students not having English as their mother tongue.
RESEARCH ENVIRONMENT. The successful PhD student will join a vibrant group of young researchers in the homogeneous catalysis laboratory at QMUL, a modern and well-equipped laboratory hosting several groups of research on organic, inorganic and organometallic chemistry. This varied group will provide excellent opportunities for learning and discovering new areas of research in homogeneous catalysis and organic synthesis. The laboratory is located in the Joseph Priestley building, in the Mile End campus of Queen Mary University, a beautiful area next to Mile End and Victoria parks in the heart of East London.
References
P. J. Chirik, Acc. Chem. Res. 2015, 48, 1687
M. D. Greenhalgh, A. S. Jones, S. P. Thomas, Chem. Cat. Chem. 2015, 7, 190
K. D. Nguyen, B. Y. Park, T. Luong, H. Sato, V. J. Garza, M. J. Krische, Science 2016, 354, 300
D. Schilter, J. M. Camara, M. T. Huynh, S. Hammes-Schiffer, T. B. Rauchfuss, Chem. Rev. 2016, 116, 8693
Selected papers by Dr Cambeiro
X. C. Cambeiro, N. Ahlsten, I. Larrosa, J. Am. Chem. Soc. 2015, 137, 15636
X. C. Cambeiro, T. C. Boorman, P. Lu, I. Larrosa, Angew. Chem. Int. Ed. 2013, 52, 1781
M. Simonetti, G. J. P. Perry, X. C. Cambeiro, F. Juliá-Hernández, J. N. Arokianathar, I. Larrosa, J. Am. Chem. Soc. 2016, 138, 3596
P. Ricci, K. Krämer, X. C. Cambeiro, I. Larrosa, J. Am. Chem. Soc. 2013, 135, 13258
E. Alza, X. C. Cambeiro, C. Jimeno, M. A. Pericàs, Org. Lett. 2007, 9, 3717