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

该提案的目的是使用先进的NMR方法研究纳米颗粒和模型有机金属配合物的配位领域中的氢、有机分子和新型配体的结构、结合、反应性和流动性。这些材料将在Bruno Chaudret的图卢兹小组中合成，Bruno Chaudret还使用分析本体和表面技术如TEM、HREM、EELS、XRD、WAXS、SAXS、XPS、IR表征这些材料。探索了对各种反应的催化活性。Hans H. Limbach和Gerd Buntkowsky将使用先进的NMR技术研究这些化合物和材料，例如变温1H，2 H，13 C固态高分辨率，偶极和四极NMR，以及通过液态NMR研究模型复合物。使用这些方法，结合，流动性和反应性的氢，配体，和移动的有机客人，包括潜在的s-键的配体，如硅烷在配位领域，特别是钌的研究。主要目标是表征氢结合位点，氢量子和经典交换，氢氧化加成/还原消除和扩散，金属催化的o/p-H2 -转换通过偶极相互作用和通过二氢分裂的机制，吸附在纳米颗粒上的有机客体分子的结构和流动性，最后理解纳米颗粒催化活性的基本步骤。Gerd Buntkowsky小组将开发上述过程中核自旋动力学的理论模型。

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.