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

本课题的目的是利用先进的核磁共振方法研究氢、有机分子和新型配体在纳米粒子和模型有机金属配合物配位球中的结构、结合、反应性和迁移率。这些材料将在Bruno Chaudret的图卢兹小组中合成，Bruno Chaudret还使用分析体和表面技术（如TEM， HREM， EELS， XRD， WAXS， SAXS， XPS， IR）对这些材料进行表征。探讨了对多种反应的催化活性。柏林的Hans H. Limbach和Gerd Buntkowsky小组将使用先进的核磁共振技术研究这些化合物和材料，例如变温度1H， 2H， 13C固态高分辨率，偶极和四极核磁共振，以及液态核磁共振模型复合物。利用这些方法，研究了氢、配体和可移动的有机客体（包括潜在的s键配体如硅烷）在配位球特别是钌中的结合、迁移性和反应性。主要目的是表征氢的结合位点、氢的量子交换和经典交换、氢的氧化加成/还原消除和扩散、金属通过偶极相互作用和双氢分裂催化o/p-H2 -转化的机理、有机客体分子吸附在纳米颗粒上的结构和迁移率，最后了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.