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Reference : UMR5069-DIDBOU0-011
Workplace : TOULOUSE
Date of publication : Friday, April 30, 2021
Type of Contract : FTC Scientist
Contract Period : 12 months
Expected date of employment : 1 September 2021
Proportion of work : Full time
Remuneration : Gross salary, from 2648 to 3938€ / month according to experience
Desired level of education : PhD
Experience required : Indifferent
- bibliographic searches and analyses
- design synthetic routes to new Cyclometallated Au(III) Complexes
- synthesis, purification and caracterisation of Cyclometallated Au(III) Complexes
- study of their properties (optical, redox, reactivity)
- reporting, preparation of supporting information (experimental procedures & analytical data), drafting of publications
- preparation, caracterisation and study of Cyclometallated Au(III) Complexes
The candidate should be well-trained in the synthesis, purification and caracterisation of organometallic complexes. Expertise in (photoredox) catalysis , electrochemistry, EPR and DFT calculations would be a plus, but is not mandatory. The candidate should have a good sense of communication (oral and written), including in English.
Environment: The LHFA is affiliated to CNRS and UPS. It is located in the chemistry building of UPS, 118 route de Narbonne, Toulouse.
The LHFA gathers 6 research teams (about 70-80 people). Its core activity is the synthesis and study of original molecules, highly reactive species.
Host team: LBPB, see the corresponding website for more details
Constraints and risks
Nothing to declare
The research in our group is focused on the development and understanding of new classes of main-group compounds (P, B…) and transition metal complexes (Au, Pd…), as well as their application in small molecule activation and catalysis. In one of our research lines, we take advantage of ligand design to stabilize highly reactive gold complexes (carbenes…), to emulate unprecedented reactivity at gold (such as oxidative addition…) and to develop new gold-catalyzed transformations. This post-doctoral project aims at exploring and advancing these three facets of gold chemistry on (P,C)-cyclometallated Au(III) complexes.
1. New reactive (P,C)-cyclometallated Au(III) complexes
We have shown that P-chelation assisted oxidative addition provides efficient access to (P,C)-cyclometallated Au(III) complexes from peri-halogenated naphthyl phosphines (J. Am. Chem. Soc. 2014, 136, 1778). This rigid backbone imparts high stability while maintaining two reactive sites at gold. It was leveraged to prepare and fully characterize unusual Au(III) species, in particular C–H agostic, pi-arene and pi-allyl complexes (Angew. Chem. Int. Ed. 2016, 55, 3414; Chem. Sci. 2017, 8, 4539; Angew. Chem. Int. Ed. 2020, 59, 1511). This is the first aim of the project to generalize this approach, varying the structure of the cyclometallated ligand and targeting new reactive Au(III) complexes.
2. New reactivity paths at Au(III)
The (P,C)-cyclometallated Au(III) complexes have also proved highly reactive, and elementary transformations unprecedented for gold such as migratory insertion of alkenes and beta-H elimination were substantiated (Angew. Chem. Int. Ed. 2015, 54, 1266; J. Am. Chem. Soc. 2016, 138, 11920). With the new cyclometallated Au(III) complexes in hands, thorough reactivity studies will be carried out to identify systems and conditions in which Au(III) engages in new reaction paths. Particular interest will be devoted to sigma-metathesis and metal-ligand cooperativity as this may offer new possibilities for activation of strong bonds and inert molecules at gold.
3. Catalytic applications of Au(III) complexes
The third objective is to take advantage of the new reactive Au(III) complexes and reactivity paths at Au(III) in catalysis. Here, Au(III) catalysis will be first targeted, as it is still underdeveloped (For application of (P,C)-cyclometallated Au(III) complexes in the hydroarylation of alkynes, see: Angew. Chem. Int. Ed. 2018, 57, 11732). Dual approaches combining Au(III) complexes and other activation modes (metal-ligand cooperativity, photo and/or redox catalysis) will also be investigated.
Expected start: september 2021. Applications should include a CV and motivation letter + the names and contacts details of at least two persons to be contacted for references.
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