Metal-mediated C-F bond activation and C-F bond formation
Recruting institution: CNRS
Diploma-delivering institutions: UPS, UoY
Thesis co-directors: Antoine Simonneau (LCC, Toulouse, FR), John Slattery and Jason Lynam (UoY, York, UK)
Secondment host: Italmatch Chemicals (IT)
The selective synthesis of fluorinated organic compounds is crucial for our modern world, as they are ubiquitous in pharmaceuticals, agrochemicals, medical imaging, materials and more. All processes leading to fluorinated chemicals involve the challenges of C–F bond activation, formation and/or functionalisation. This project aims to understand key mechanisms by which transition metal complexes selectively mediate such transformations, experimentally and theoretically, and translate this knowledge into novel, rationally designed catalysts. Complementary early (ETM) and late (LTM) transition metal organometallic approaches will lead to the development of original bimetallic, cooperative fluorination/C–F bond activation catalyses.
 Q. Dufrois, N. Romero, N. Crespo, A. Pujol, L. Vendier, M. Etienne, in preparation.
 L. M. Milner, N. E. Pridmore, A. C. Whitwood, J. M. Lynam, J. M. Slattery, J. Am. Chem. Soc., 2015, 137, 33, 10753–10759; b) L. M. Hall, D. P. Tew, N. E. Pridmore, A. C. Whitwood, J. M. Lynam, J. M. Slattery, Angew. Chem. Int. Ed., 2017, 56, 7551-7556.
(1) Demonstration of fluoride transfer to ETM from at least 5 different fluorinated aromatics leading to CC coupling with a different selectivity to that for LTM, and catalytic implementation of this elementary step. (2) Insight into stoichiometric fluoride and F+ transfer reactions necessary for a catalytic cycle using analogous approaches for a selection of 10 ETM and LTM complexes. (3) Unifying these approaches to add multiple fluorine atoms by sequential electrophilic/nucleophilic fluorinations to provide viable catalytic cycles to a family of highly valuable, partially fluorinated materials in high yield (>90 %) and efficiency
PhD student - ESR5
Sara Bonfante obtained her Master’s degree in Chemistry at the University of Padova, Italy, in 2019. There, she conducted research in the laboratory of Professor A. Biffis on catalysed hydroarylation reactions conducted in ionic liquids. She then spent a few months at the LHFA laboratory in Toulouse, under the supervision of Dr D. Bourissou, investigating gold(I) complexes featuring a Au•••H-N hydrogen bond. Her PhD research is focused on C-F bond formation and activation with organometallic reagents.