Heterometallic Mg−Ba Hydride Clusters in Hydrogenation Catalysis
Heterometallic Mg−Ba Hydride Clusters in Hydrogenation Catalysis
复制标题
DOI：
10.1002/cctc.202101071
复制
发表时间：
2021-09
期刊：
影响因子：
4.5
通讯作者：
Michael Wiesinger;Christian Knüpfer;Holger Elsen;Jonathan Mai;J. Langer;S. Harder
中科院分区：
文献类型：
--
作者：
Michael Wiesinger;Christian Knüpfer;Holger Elsen;Jonathan Mai;J. Langer;S. Harder
MgN“2/BaN”2 混合物 (N“=N(SiMe3)2) 与 PhSiH3 反应，得到三种独特的异金属 Mg/Ba 氢化物簇：Mg5Ba4H11N”7 ⋅ (苯)2 (1)、Mg4Ba7H13N“9 ⋅ (甲苯)2 (2) 和 Mg7Ba12H26N”12 (3)。产品形成由 Mg/Ba 比例和温度控制。描述了晶体结构。虽然 3 完全不溶，但簇 1 和 2 在芳香族溶剂中保留其结构。 DFT 计算和 AIM 分析表明具有 Mg−H 和 Ba−H 键路径的高度离子键合。还观察到不寻常的 H−⋅⋅⋅H− 键路径。研究了MgN“2、BaN”2以及MgN“2/BaN”2混合物的催化加氢反应。而MgN“2仅在亚胺加氢中具有活性，而烯烃和炔烃加氢则需要Ba的存在。MgN”2/BaN“2混合物的催化活性一般介于其单个组分的催化活性之间，并且强协同效应并不明显。
Reaction of a MgN“2/BaN”2 mixture (N“=N(SiMe3)2) with PhSiH3 gave three unique heterometallic Mg/Ba hydride clusters: Mg5Ba4H11N”7 ⋅ (benzene)2 (1), Mg4Ba7H13N“9 ⋅ (toluene)2 (2) and Mg7Ba12H26N”12 (3). Product formation is controlled by the Mg/Ba ratio and temperature. Crystal structures are described. While 3 is fully insoluble, clusters 1 and 2 retain their structures in aromatic solvents. DFT calculations and AIM analyses indicate highly ionic bonding with Mg−H and Ba−H bond paths. Also unusual H−⋅⋅⋅H− bond paths are observed. Catalytic hydrogenation with MgN“2, BaN”2 and the mixture MgN“2/BaN”2 has been studied. Whereas MgN“2 is only active in imine hydrogenation, alkene and alkyne hydrogenation needs the presence of Ba. The catalytic activity of the MgN”2/BaN“2 mixture lies in general between that of its individual components and strong cooperative effects are not evident.