| Institution: | 1. Technical University of Munich, TUM School of Natural Sciences, Department of Chemistry, Chair of Inorganic and Metal-Organic Chemistry, Lichtenbergstraße 4, 85748 Garching, Germany;2. Univ Rennes, CNRS, ISCR-UMR 6226, 35000 Rennes, France;3. Department of Pharmacy, Ludwig-Maximilians-University Munich, Butenandtstrasse 7, 81377 Munich, Germany;4. Technical University of Munich, TUM School of Natural Sciences, Department of Chemistry, Chair of Inorganic and Metal-Organic Chemistry, Lichtenbergstraße 4, 85748 Garching, Germany
Catalysis Research Centre, Technical University Munich, Ernst-Otto-Fischer Straße 1, 85748 Garching, Germany |
| Abstract: | The bimetallic, decanuclear Ni3Ga7-cluster of the formula Ni3(GaTMP)3(μ2-GaTMP)3(μ3-GaTMP)] ( 1 , TMP=2,2,6,6-tetramethylpiperidinyl) reacts reversibly with dihydrogen under the formation of a series of (poly-)hydride clusters 2 . Low-temperature 2D NMR experiments at −80 °C show that 2 consist of a mixture of a di- ( 2Di ), tetra- ( 2Tetra ) and hexahydride species ( 2Hexa ). The structures of 2Di and 2Tetra are assessed by a combination of 2D NMR spectroscopy and DFT calculations. The cooperation of both metals is essential for the high hydrogen uptake of the cluster. Polyhydrides 2 are catalytically active in the semihydrogenation of 4-octyne to 4-octene with good selectivity. The example is the first of its kind and conceptually relates properties of molecular, atom-precise transition metal/main group metal clusters to the respective solid-state phase in catalysis. |
