Gutmann, T. ; Walaszek, B. ; Xu, Y. P. ; Wächtler, M. ; Del Rosal, I. ; Grünberg, A. ; Poteau, R. ; Axet, R. ; Lavigne, G. ; Chaudret, B. ; Limbach, H. H. ; Buntkowsky, G. (2010)
Hydrido-Ruthenium Cluster Complexes as Models for Reactive Surface Hydrogen Species of Ruthenium Nanoparticles. Solid-State H-2 NMR and Quantum Chemical Calculations.
In: Journal of the American Chemical Society, 132 (33)
doi: 10.1021/ja104229a
Artikel, Bibliographie
Kurzbeschreibung (Abstract)
The H-2 quadrupolar interaction is a sensitive tool for the characterization of deuterium-metal binding states. In the present study, experimental solid-state H-2 MAS NMR techniques are used in the investigations of two ruthenium clusters, D4Ru4(CO)(12) (1) and D2Ru6(CO)(18) (2), which serve as model compounds for typical two-fold, three-fold, and octahedral coordination sites on metal surfaces. By line-shape analysis of the H-2 MAS NMR measurements of sample 1, a quadrupolar coupling constant of 67 +/- 1 kHz, an asymmetry parameter of 0.67 +/- 0.1, and an isotropic chemical shift of -17.4 ppm are obtained. In addition to the neutral complex, sample 2 includes two ionic clusters, identified as anionic DRu6(CO)(18)(-) (2(-)) and cationic D3Ru6(CO)(18)(+) (2(+)). By virtue of the very weak quadrupolar interaction (<2 kHz) and the strong low-field shift (+16.8 ppm) of 2(-), it is shown that the deuteron is located in the symmetry center of the octahedron spanned by the six ruthenium atoms. For the cationic 2(+), the quadrupolar interaction is similar to that of the neutral 2. Quantum chemical DFT calculations at different model structures for these ruthenium clusters were arranged in order to help in the interpretation of the experimental results. It is shown that the H-2 nuclear quadrupolar interaction is a sensitive tool for distinguishing the binding state of the deuterons to the transition metal. Combining the data from the polynuclear complexes with the data from mononuclear complexes, a molecular ruler for quadrupolar interactions is created. This ruler now permits the solid-state NMR spectroscopic characterization of deuterium adsorbed on the surfaces of catalytically active metal nanoparticles.
| Typ des Eintrags: | Artikel |
|---|---|
| Erschienen: | 2010 |
| Autor(en): | Gutmann, T. ; Walaszek, B. ; Xu, Y. P. ; Wächtler, M. ; Del Rosal, I. ; Grünberg, A. ; Poteau, R. ; Axet, R. ; Lavigne, G. ; Chaudret, B. ; Limbach, H. H. ; Buntkowsky, G. |
| Art des Eintrags: | Bibliographie |
| Titel: | Hydrido-Ruthenium Cluster Complexes as Models for Reactive Surface Hydrogen Species of Ruthenium Nanoparticles. Solid-State H-2 NMR and Quantum Chemical Calculations |
| Sprache: | Englisch |
| Publikationsjahr: | 2010 |
| Titel der Zeitschrift, Zeitung oder Schriftenreihe: | Journal of the American Chemical Society |
| Jahrgang/Volume einer Zeitschrift: | 132 |
| (Heft-)Nummer: | 33 |
| DOI: | 10.1021/ja104229a |
| Kurzbeschreibung (Abstract): | The H-2 quadrupolar interaction is a sensitive tool for the characterization of deuterium-metal binding states. In the present study, experimental solid-state H-2 MAS NMR techniques are used in the investigations of two ruthenium clusters, D4Ru4(CO)(12) (1) and D2Ru6(CO)(18) (2), which serve as model compounds for typical two-fold, three-fold, and octahedral coordination sites on metal surfaces. By line-shape analysis of the H-2 MAS NMR measurements of sample 1, a quadrupolar coupling constant of 67 +/- 1 kHz, an asymmetry parameter of 0.67 +/- 0.1, and an isotropic chemical shift of -17.4 ppm are obtained. In addition to the neutral complex, sample 2 includes two ionic clusters, identified as anionic DRu6(CO)(18)(-) (2(-)) and cationic D3Ru6(CO)(18)(+) (2(+)). By virtue of the very weak quadrupolar interaction (<2 kHz) and the strong low-field shift (+16.8 ppm) of 2(-), it is shown that the deuteron is located in the symmetry center of the octahedron spanned by the six ruthenium atoms. For the cationic 2(+), the quadrupolar interaction is similar to that of the neutral 2. Quantum chemical DFT calculations at different model structures for these ruthenium clusters were arranged in order to help in the interpretation of the experimental results. It is shown that the H-2 nuclear quadrupolar interaction is a sensitive tool for distinguishing the binding state of the deuterons to the transition metal. Combining the data from the polynuclear complexes with the data from mononuclear complexes, a molecular ruler for quadrupolar interactions is created. This ruler now permits the solid-state NMR spectroscopic characterization of deuterium adsorbed on the surfaces of catalytically active metal nanoparticles. |
| Freie Schlagworte: | gaussian-basis sets dft calculations hartree-fock atoms li adsorption density shifts c-13 v-51 1st-principles |
| Zusätzliche Informationen: | 640QL Times Cited:13 Cited References Count:60 |
| Fachbereich(e)/-gebiet(e): | 07 Fachbereich Chemie 07 Fachbereich Chemie > Eduard Zintl-Institut > Fachgebiet Physikalische Chemie |
| Hinterlegungsdatum: | 27 Okt 2014 20:42 |
| Letzte Änderung: | 13 Sep 2021 10:25 |
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