The immobilization of organo‐ and metal catalysts on dendrimers and nanoparticles towards the development of sustainable chemical processes is proposed in this collaborative project. The groups involved are investigating a number of different catalytic processes that form the basis of the joint efforts envisaged here. The focus of this collaborative project is on evaluating supports with globular structures (dendrimers, nanoparticles) to arrive at catalysts that can be employed in continuous setups using nanofiltration techniques. Applying these techniques catalytic transformations aiming at the conversion of furans, i.e. renewable resources, to arenes and coupling reactions of arenes will be investigated. Moreover the use of safe arylating agents (triarylbismuths), and “green” Lewis acids ( Rare Earth triflates) will be investigated in reactions of industrial interest.

We propose studying the interplay between consumption and income inequality over the life cycle in France and the U.S. over the last thirty years. On the one hand, the four quantitative analyses in this project provide direct descriptive evidence based on micro data of the change in consumption inequality. On the other hand, they incorporate economic theoretical models shedding light on economic mechanisms at stake generating inter-individual dispersion in consumption levels. The project can be incorporated in Axe thématique 2: Génèse et dynamique des inégalités from the ANR call for project inégalité-inégalités. The studies detailed below concentrate on the same topics but tackle the issue from different perspectives. They blend micro-econometric, macro general equilibrium and theoretical economic models studying consumption inequality. More precisely, in the first project we assess the share of risk in the consumption distribution. In the second approach we target at measuring the degree of consumption risk-sharing in these economies that the financial market permits. In the third project we endogenize the dispersion of earnings leading to the spreading consumption levels using a human capital model. Finally, in step four, we derive the implications of a policy aiming at correcting consumption and wealth inequalities. These contributions are joint work realized by a team of four researchers with strong quantitative and complementary skills. Finally, the team has yet never benefited from any external funding to develop our research.

Transition-metal catalysts with a versatile coordination mode and reactivity, allowing highly efficient and selective reactions under mild conditions, are indispensable in actual organic synthesis. However, in spite of the significant importance of organometallic catalysts, the principal problem is the highly limited natural resource of precious transition metals. This project principally concerns the use of silicon (the second most abundant element in the Earth’s crust) as catalyst instead of transition metals. Although the importance of its abundance is well recognized in material chemistry, as it can be seen by the vast world production of silicon based materials (polymers, rubber, semiconductors), real success in chemistry with such a vision has never been achieved. This is probably due to the lack of appropriate stable silicon species with particular and highly modulable electronic properties which can be applied for various catalytic systems. For this purpose, low-valent silicon(II) complexes should be the most promising candidates, due to their particular coordination properties in contrast to other high valent silicon species with simple reactivity (classical Lewis acid). Another great advantage of these complexes is their structural flexibility, compared to the previously known extremely reactive low-valent species. We propose, in this project, the development of new stable low-valent silicon(II) complexes as “resource-problem-free catalysts” with a transition metal like behavior. The success of this project should open a new wide research domain in chemistry and could change the vision of catalysis.

N-Heterocyclic carbenes (NHCs) have become widely used ligands since the beginning of this century. They are compatible with most transition metals and generally lead to air-stable and thermally robust complexes which do not undergo ligand dissociation. More importantly, they have shown a great potential in homogeneous catalysis, and there is more and more evidence in the literature that these ligands can outperform phosphanes in catalytic activity. My major preoccupation, since the beginning of my independent research activities in 2003, has been to design bifunctional ligands for the generation of air-stable, robust catalysts – with the help of the substitutionally inert NHC moiety, that would keep an optimal activity with the presence of a second, more labile coordinating unit. The strength of NHC ligands is their structural versatility: they can easily be functionalised. Thus, we can consider the introduction of chirality – via a chiral centre or planar chirality, of hydrosoluble groups, or even of electroactive units. According to the metal and medium chosen, the ligands can find applications in catalytic reactions for fine chemicals synthesis (asymmetric C-C coupling), or of industrial importance (hydroamination). They can also help us understand specific reactivity issues, for example with the use of redox-switchable hemilabile ligands in isomerisation reactions. This project will follow three directions. In the first part we will develop bifunctional, chiral ligands, and study their coordination chemistry, mainly with nickel and palladium. The metal complexes will be tested in asymmetric C-C coupling reactions, such as Kumada-Corriu and Suzuki reactions, with the help of an expert in asymmetric catalysis. The second topic will deal with the application of new NHC ligands in the intermolecular hydroamination of non-activated alkenes. The activity of both achiral and chiral rhodium(I) and iridium(I) complexes will be evaluated in the hydroamination of ethylene and hexane with aniline, in collaboration with a hydroamination specialist. Finally, the third part of the project will be devoted to the development of redox-active hemilabile NHC ligands and coordination studies with rhodium(I) or ruthenium(II). The redox behaviour of both ligands and complexes will be studied by electrochemical methods, and their potential as isomerisation catalysts will be investigated.