Eight-electron Pt/Cu superatom encapsulating three “electron-donating” hydrides

作者：Ayisha He, Dongjie Zuo, Guangmei Jiang, Xiongkai Tang, Lin Wang, Liubin Feng, Zaiwang Zhao, Jianyu Wei, Nanfeng Zheng, Hui Shen · 发表于：Science Advances · 年份：2025 · DOI：10.1126/sciadv.ads4488 · 被引用次数：14 · 研究领域：Nanocluster Synthesis and Applications、Nanomaterials for catalytic reactions、Pharmacological Effects and Toxicity Studies

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, PtH 3 Cu 23 (iso-propyl-PhS) 18 (PPh 3 ) 4 (PtH 3 Cu 23 ), which contains three interstitial electron-donating hydrides. The molecular structure of PtH 3 Cu 23 describes the encapsulation of a PtCu 12 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 PtH 3 Cu 23 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.