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PhD position (M/W) Carboranyl phosphines meet dendrimers: Electron-deficient scaffolds for ligand design and applications in catalysis.

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Français - Anglais

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General information

Reference : UPR8241-ANNCAM-001
Workplace : TOULOUSE
Date of publication : Tuesday, March 17, 2020
Scientific Responsible name : Anne-Marie Caminade
Type of Contract : PhD Student contract / Thesis offer
Contract Period : 36 months
Start date of the thesis : 1 October 2020
Proportion of work : Full time
Remuneration : 2 135,00 € gross monthly

Description of the thesis topic

Dendrimers are hyperbranched macromolecules, and the specialty of the Toulouse group. The surface of dendrimers can be decorated with any type of function to fulfil the required properties. Carboranyl phosphines, for which the Leipzig group is expert, are tunable ligands, for which the steric and electronic properties can be modified at will. Anchoring these ligands to the surface of dendrimers will offer, for the first time, dendrimer-based electron-deficient carboranyl bis-phosphines or mixed (hemilabile) carboranyl phosphine-amines, -alkoxides, -thiols or -thioethers, etc. as ligands for challenging catalytic transformations. C–C coupling and C–H activation will be studied in detail. Decrease in the metal leaching will be particularly targeted, the objective being leaching < 1 ppm. The effects of different dendrimer structures and metals employed on the reactivity, activity, and selectivity of the catalysts will be studied, rationalized in collaboration with a theoretical group in Barcelona through secondment and applied for a rational design of improved catalysts. The most efficient functionalized dendrimers will be scaled up and tested on industrial reactions at the company BASF, Germany. More information can be found at: http://www.ccimc.eu/esr12-project/

Work Context

This thesis is part of an Innovative Training Network (ITN) and more specifically a European Joint Doctorate (EJD), funded by the European Commission through the Marie Sklodowska-Curie Action (MSCA), entitled "Coordination Chemistry Inspires Molecular Catalysis" (CCIMC). This programme involves 15 joint doctoral theses. You are encouraged to consider all 15 thesis projects; information is available on the ITN-EJD website at www.ccimc.eu.
This offer is a 3 year, fully-funded double doctorate programme between the Laboratoire de Chimie de Coordination (LCC), in the Dendrimers and Heterochemistry group in Toulouse (FR) and the Institut für Anorganische Chemie of Leipzig University (ULEI, DE). You will be co-supervised by Dr. Anne-Marie Caminade in Toulouse and by Prof. Dr. Evamarie Hey-Hawkins in Leipzig, during 15 months in each laboratory. In addition, two secondments, of 3 months each, are scheduled in Barcelona, Spain, with Agustí Lledós at UAB, and in Ludwigshafen, Germany, at BASF. Furthermore, training events will take place at a number of sites around Europe, allowing the doctoral researcher to benefit from significant international mobility.
The Laboratoire de Chimie de Coordination (LCC), located in Toulouse, southern France, associated to the Université Paul Sabatier, is the CNRS (Centre National de la Recherche Scientifique) flagship institution in coordination chemistry, and one of the top chemistry institutes in France. Strong of more than 100 persons, including researchers and technicians, divided in 15 teams, the LCC offers an expertise in the molecular chemistry of transition-metal and main group elements with specific research interests to solve current issues associated with climate change, energy transition and life sciences along 3 main axes of investigations: catalysis, materials and health. The LCC has close partnerships with a number of public and private enterprises in France, Europe, and over the world. More than 100 undergraduates, graduates and postgraduates of various nationalities are present at the LCC, thus ensuring a motivating working environment as well as opportunities for social events. We have at our disposal laboratory space and benches fully equipped with separate fume hoods and high-vacuum lines, as well as very well equipped technical and analytical platforms for the daily support of scientific work. All the accessible instrumental equipment belongs to and is maintained by the CNRS-LCC and the Institut de Chimie de Toulouse, in the form of several characterisation platforms, each one staffed by well-trained top-notch technicians. They comprise: NMR (8 instruments up to 800 MHz including solid state), X-ray diffraction (3 single-crystal and one powder), microscopy (12 SEM/TEM/AFM instruments), MS (all methods), 2 SQUID magnetometers, Mössbauer, GC-MS, HPLC (including chiral semi-preparative), electrochemistry, optical spectroscopy including Raman, etc.
Leipzig University, which was founded in 1409, today has about 30,000 students. There are 14 faculties, covering topics from medicine to natural sciences, from mathematics to theology and from social sciences to sports. This variety enables each scientist to make use of the knowledge of more than 400 professors and hence to work in interdisciplinary projects. The group has ca. 600 m2 laboratory space and benches fully equipped with separate fume cupboards for at least 34 co-workers and 4 specially equipped labs with a wealth of instrumentation for characterisation. Thus, all equipment necessary for state-of-the-art synthesis, including high-vacuum lines and Schlenk techniques (also an MBRAUN Solvent Purification System MB SPS- 800), as well as equipment for purification of compounds (column chromatography, HPLC, two Isolera 4) etc. is available. Advanced characterisation techniques, including GC-MS (QP-2010, Shimadzu), 2 NMR machines (also heteronuclear NMR; Bruker AVANCE DRX 400 spectrometer) equipped with VT devices, UV-Vis, IR (ATR), Raman, DTA/TG/DSC and single-crystal X-ray diffraction (Gemini diffractometer (Agilent Technologies)) are also available. Further equipment is provided by the department, such as service for elemental analysis and mass spectrometry.
The candidate should have a strong background in synthetic chemistry, and must be enthusiastic about, and willing to, travel as part of the project and must accept the terms of the award of the double degree, including the requirement to attend international training events and fulfil the double degree examination process. There will be extensive opportunities to engage with other groups in the consortium, who represent many of the European leaders in the area of coordination chemistry and catalysis.

Constraints and risks

Please pay attention that to be eligible, on 1st October 2020, the candidate must be in the first four years (full-time equivalent research experience) of her/his research career and has not been awarded a doctoral degree. On 1st October 2020, she/he must not have resided or carried out her/his main activity (work, studies, etc.) in France for more than 12 months in the preceding 3 years.

Additional Information

The CCIMC ITN consortium addresses the current lack of coordinated doctoral training at the European level on molecular catalysis. It aims to push the frontiers of knowledge in ligand design, coordination chemistry, pre-catalyst development, catalyst recovery and catalytic process implementation, while also offering full scale training in professional and personal transferable skills, to prepare a new generation of junior scientists to meet the economic and societal challenges of the chemical industry in the 21st century.

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