He Ayisha, Zuo Dongjie, Jiang Guangmei, Tang Xiongkai, Wang Lin, Feng Liubin, Zhao Zaiwang, Wei Jianyu, Zheng Nanfeng, Shen Hui
College of Energy Materials and Chemistry, Inner Mongolia University, Hohhot 010021, China.
New Cornerstone Science Laboratory, State Key Laboratory for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, and National and Local Joint Engineering Research Center of Preparation Technology of Nanomaterials, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
Sci Adv. 2025 Jan 10;11(2):eads4488. doi: 10.1126/sciadv.ads4488. Epub 2025 Jan 8.
Hydrides in metal complexes or nanoclusters are typically viewed as electron-withdrawing. Several recent reports have demonstrated the emergence of "electron-donating" hydrides in tailoring the structure, electronic structure, and reactivity of metal nanoclusters. However, the number of such hydrides included in each cluster kernel is limited to one or two. There is even no structure model, neither theoretical nor experimental, for encapsulating a third electron-donating hydride into one cluster entity. Here, we present a structurally precise superatomic nanocluster, PtHCu(iso-propyl-PhS)(PPh) (PtHCu), which contains three interstitial electron-donating hydrides. The molecular structure of PtHCu describes the encapsulation of a PtCu core that contains three interstitial hydrides in a distorted anticuboctahedral architecture, in an outer sphere consisting of copper atoms and thiolate and phosphine ligands. Density functional theory calculations reveal that the three hydrides in PtHCu contribute their valence electrons to the cluster superatomic electron count of eight. In this regard, the cluster represents a rare Pt-included copper-hydride superatom with eight free electrons.
金属配合物或纳米团簇中的氢化物通常被视为吸电子的。最近的几份报告表明，在定制金属纳米团簇的结构、电子结构和反应活性时，出现了“供电子”氢化物。然而，每个团簇核心中包含的此类氢化物数量限制为一两个。甚至没有将第三个供电子氢化物封装到一个团簇实体中的结构模型，无论是理论上的还是实验上的。在此，我们展示了一种结构精确的超原子纳米团簇，PtHCu(异丙基 - 苯硫醚)(三苯基膦)(PtHCu)，它包含三个间隙供电子氢化物。PtHCu的分子结构描述了一个PtCu核心的封装情况，该核心在由铜原子以及硫醇盐和膦配体组成的外层球壳中，以扭曲的反立方八面体结构包含三个间隙氢化物。密度泛函理论计算表明，PtHCu中的三个氢化物将其价电子贡献给了团簇超原子的八个电子数。在这方面，该团簇代表了一种罕见的包含铂的具有八个自由电子的氢化铜超原子。
