The goal of this PhD was to elaborate supported Ru-NHC catalytic materials based on hybrid organic-inorganic materials having imidazolium units perfectly distributed within a silica matrix. Passivation of these imidazolium materials followed by formation of NHC-carbene and reaction with [RuCl2(p-cymene)]2 provided these well-defined surface sites of general structures RuCl2(NHC)(L), where L was para-cymene (p-cymene) or THF depending on the reaction conditions, which could be further replaced by PMe3. These systems were then tested in the hydrogenation of CO2 in presence of amine to give formamides. The mono-NHC systems were highly active only in the presence of PMe3 ligands, but suffered from Ru leaching, evidencing the low stability of the NHC-Ru bond under the reaction conditions. On the other hand, dinuclear bis-NHC Ru systems were also developed, and they displayed much improved activity and stability in the hydrogenation of CO2 in the presence of PMe3 compared to the mono-NHC systems. This allowed the use of much higher reaction temperatures (200 °C) and provided heterogeneous catalysts with performances close to those obtained with the best homogeneous catalysts, Cl2Ru(dppe)2.
