From Molecular Complexes to Complex Metallic Nanostructures—2H Solid‐State NMR Studies of Ruthenium‐Containing Hydrogenation Catalysts

Abstract In the last years, the combination of 2 H solid‐state NMR techniques with quantum‐chemical calculations has evolved into a powerful spectroscopic tool for the characterization of the state of hydrogen on the surfaces of heterogeneous catalysts. In the present minireview, a brief summary of this development is given, in which investigations of the structure and dynamics of hydrogen in molecular complexes, clusters and nanoparticle systems are presented, aimed to understand the reaction mechanisms on the surface of hydrogenation catalysts. The surface state of deuterium/hydrogen is analyzed employing a combination of variable‐temperature 2 H static and magic‐angle spinning (MAS) solid‐state NMR techniques, in which the dominant quadrupolar interactions of deuterium give information on the binding situation and local symmetry of deuterium/hydrogen on molecular species. Using a correlation database from molecular complexes and clusters, the possibility to distinguish between terminal RuD, bridged Ru 2 D, three‐fold Ru 3 D, and interstitial Ru 6 D is demonstrated. Combining these results with quantum‐chemical density functional theory (DFT) calculations allows the interpretation of 2 H solid‐state data of complex “real world” nanostructures, which yielded new insights into reaction pathways at the molecular level.