Metal Nanoparticles as Novel Organometallic Objects: Synthesis and NMR Studies of the Structure, Binding, Mobility and Reactivity of Hydrogen and Organic Molecules in their Coordination Sphere

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The objective of this proposal is to study the structure, binding, reactivity and mobility of hydrogen, organic molecules and novel ligands in the coordination sphere of nanoparticles and model organometallic complexes using advanced NMR methods. The materials will be synthesized in the Toulouse group of Bruno Chaudret who also characterizes these materials using analytical bulk and surface techniques such as TEM, HREM, EELS, XRD, WAXS, SAXS, XPS, IR. The catalytic activity towards a variety of reactions is explored. The Berlin groups of Hans H. Limbach and Gerd Buntkowsky will study these compounds and materials using advanced NMR techniques, such as variable temperature 1H, 2H, 13C solid state high resolution, dipolar and quadrupolar NMR, and for model complexes by liquid state NMR. Using these methods, the binding, mobility and reactivity of hydrogen, ligands, and mobile organic guests including potential s-bond ligands such as silanes in the coordination sphere especially of Ru are studied. Main objectives are the characterization of hydrogen binding sites, hydrogen quantum and classical exchange, hydrogen oxidative addition/reductive elimination and diffusion, the mechanism of the metal catalyzed o/p-H2 - conversion via dipolar interactions and via dihydrogen splitting, the structure and mobility of organic guest molecules absorbed on nanoparticles, and finally the understanding of elementary steps of the catalytic activity of nanoparticles. The group of Gerd Buntkowsky will develop theoretical models for the dynamics of the nuclear spins during the above processes.