Muhr Maximilian, Liang Hao, Allmendinger Lars, Bühler Raphael, Napoli Fabrizio E, Ukaj Dardan, Cokoja Mirza, Jandl Christian, Kahlal Samia, Saillard Jean-Yves, Gemel Christian, Fischer Roland A
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.
Angew Chem Int Ed Engl. 2023 Sep 4;62(36):e202308790. doi: 10.1002/anie.202308790. Epub 2023 Jul 28.
The bimetallic, decanuclear Ni Ga -cluster of the formula [Ni (GaTMP) (μ -GaTMP) (μ -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- (2 ), tetra- (2 ) and hexahydride species (2 ). The structures of 2 and 2 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.
式为[Ni (GaTMP) (μ -GaTMP) (μ -GaTMP)]（1，TMP = 2,2,6,6 - 四甲基哌啶基）的双金属十核镍镓簇合物与氢气发生可逆反应，生成一系列（多）氢化物簇合物2。在-80°C下进行的低温二维核磁共振实验表明，2由二氢化物（2）、四氢化物（2）和六氢化物物种（2）的混合物组成。通过二维核磁共振光谱和密度泛函理论计算相结合的方法对2和2的结构进行了评估。两种金属的协同作用对于簇合物的高氢吸收至关重要。多氢化物2在4-辛炔半加氢生成4-辛烯的反应中具有催化活性，选择性良好。该实例尚属首例，从概念上将分子级、原子精确的过渡金属/主族金属簇合物的性质与催化中的相应固态相联系起来。
