Chen-Wei Liu团队报道了间隙氢化物在Cu11模板中的反应以获得双金属簇。相关研究成果于2021年11月10日发表在《德国应用化学》。

与表面氢化物形成鲜明对比的是，间隙氢化物的反应性很难探索。当用金属离子（Cu⁺、Ag⁺、Au⁺）处理时，稳定的Cu(I)二氢化物模板[Cu11H2{S2 P(OiPr）2}6(C≡CPh)3](H2-Cu11)生成三种不同的化合物；即[CuH2Cu11{S2 P(OiPr)2}6(C≡CPh)3]⁺（1），[AgH2Cu14{S2 P(OiPr)2}6((C≡CPh)6]⁺（2）和[AuCu11{S2 P(OiPr)2}6（C）≡CPh)3 Cl]（3）.1和2均为M（I）物种，并与其H2Cu11前体保持相同数量的氢化物配体。

中子衍射首次揭示了在AgCu32环境中的三角锥体氢化物配位模式。3的双金属簇不含氢化物，并呈现混合价态[AuCu11]10+金属核，使其成为双电子超原子。因此，根据M⁺的性质，H2Cu11反应物的三角锥体氢化物表现不同。在M=Cu或Ag的情况下，它们作为规则的双电子配体。在M=Au的情况下，它们作为电子给体，随着H₂的释放形成双电子超原子。

附：英文原文

Title: Reactivities of Interstitial Hydrides in a Cu11 Template: En Route to Bimetallic Clusters

Author: Rhone P. Brocha Silalahi, Qi Wang, Jian-Hong Liao, Tzu-Hao Chiu, Ying-Yann Wu, Xiaoping Wang, Samia Kahlal, Jean-Yves Saillard, Chen-Wei Liu

Issue&Volume: 2021-11-10

Abstract: In sharp contrast to that of surface hydrides, reactivities on interstitial hydrides are difficult to explore. When treated with a metal ion (Cu  +  , Ag  +  , and Au  +  ), the stable Cu(I) dihydride template [Cu  11  H  2  {S  2  P(O  i  Pr)  2  }  6  (C≡CPh)  3  ] (  H  2  Cu  11  ) generates surprisingly three very different compounds; namely [CuH  2  Cu  11  {S  2  P(O  i  Pr)  2  }  6  (C≡CPh)  3  ]  +  (  1  ), [AgH  2  Cu  14  {S  2  P(O  i  Pr)  2  }  6  ((C≡CPh)  6  ]  +  (  2  ), and [AuCu  11  {S  2  P(O  i  Pr)  2  }  6  (C≡CPh)  3  Cl] (  3  ).  1  and  2  are both M(I) species and maintain the same number of hydride ligands as their  H  2  Cu  11  precursor. Neutron diffraction revealed the first time a trigonal pyramidal hydride coordination mode in an AgCu  3  environment of  2  . The bimetallic cluster of  3  has no hydride and exhibits a mixed-valent [AuCu  11  ]  10+  metal core, making it a 2-electron superatom. Thus, depending on the nature of M  +  , trigonal pyramidal hydrides of the  H  2  Cu  11  reactant behave differently. In the cases of M = Cu or Ag, they act as regular 2-electron ligands. In the case of M = Au, they behave as electron donors, leading to the formation of a 2-electron superatom, with liberation of H  2  .

DOI: 10.1002/anie.202113266

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202113266