Imidazolium based ionic liquids (ILs) consist of a continuous 3-D network of ionic channels, coexisting with non polar domains created by the grouping of lipophilic alkyl chains, forming dispersed or continuous microphases. The aim of this work is to use the specific solvation properties of ILs, related to this 3-D organisation, to generate and stabilise in situ metal nanoparticles (NPs) of a controlled and predictable size. This approach has found application in fields such as catalysis and microelectronics. The phenomenon of crystal growth of NPs (ruthenium, nickel, tantalum) generated in situ in ILs from the decomposition of organometallic complexes under molecular hydrogen, is found not only to be controlled by i) the size of non-polar domains, in which the complexes dissolve, but also by ii) the experimental conditions (temperature, stirring) and iii) the nature of the metal and its precursor complex. The previously unexplained stabilisation mechanism of NPs in ILs is found to depend on the mechanism of formation of NPs, which may lead to the presence of either hydrides or N-heterocyclic carbenes (NHC) at their surface. These have both been evidenced through isotopic labelling experiments analysed by NMR and mass spectrometry. Another advantage of ILs is that they provide an interesting medium for catalytic reactions. Studies on the influence of the IL on the catalytic performance in homogeneous catalysis have highlighted the crucial importance of the physical-chemical parameters of ILs, in particular the viscosity, for which a term must be included in the kinetic rate law. Using these findings, a thorough investigation of the effect of the NP size on catalytic activity and selectivity in hydrogenation in ILs was undertaken, confirming the importance of controlling NP size for catalytic applications.
