Cooperative Catalysis for C-P Bond Formation, H/F

The LHFA is a joint CNRS-UPS research unit located in the UPS chemistry building, 118 route de Narbonne, Toulouse. The laboratory is made up of 5 research teams and includes around sixty people. Its core activity is the synthesis and study of original molecules, highly reactive species.

Context. Over the last decade, cooperative effects in transition metal catalysis have attracted increasing attention from the scientific community. Thanks to the synergy between two different catalytic sites, extraordinary improvements in efficiency and selectivity can be achieved. In this context, metal/ligand cooperation (MLC), in which one of the ligands participates actively to the activation of the substrates, can be highlighted.1 Pincer complexes of transition metals play an important role in this area.2 We have contributed to this field by developing an original non-innocent ligand based on an indene skeleton bearing two coordinating side-arms. Remarkable results have been obtained in catalytic cyclisation processes involving C-O/C-N & C-C bonds formation with d8 complexes based on the group 10 metals.
Objectives. Building on these successes, the aim for this PhD. project is the diversification of MLC catalysis with group 10 pincer complexes, by developing a new family of non-innocent pincer ligands. The first objective will be to prepare and characterize Ni, Pd and Pt complexes bearing the original pincer ligands, and to evidence their non-innocent behavior. We will then take advantage of this non-innocence in MLC catalysis and more particularly in the preparation of P-containing cycles via the creation of C-P bonds.
This is a multidisciplinary project involving: (i) ligand design of new non-innocent cooperative ligands, (ii) preparation, characterization (multi-dimensional NMR, X-ray diffraction, IR…) and reactivity studies of organometallic compounds and (iii) exploration of catalytic activity.
The candidate should have a good knowledge of molecular chemistry and a particular taste for organometallic / coordination chemistry. Motivation for research, curiosity and team spirit will be additional assets