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

• Published in: Angewandte Chemie International Edition 2022-01, Vol.61 (2), p.e202113266-n/a
• Main Authors: Silalahi, Rhone P. Brocha, Wang, Qi, Liao, Jian‐Hong, Chiu, Tzu‐Hao, Wu, Ying‐Yann, Wang, Xiaoping, Kahlal, Samia, Saillard, Jean‐Yves, Liu, C. W.
• Format: Article
• Language: English
• Subjects: Bimetals; cluster compounds; Copper; Core making; Dihydrides; Gold; Hydrides; Metal ions; Neutron diffraction; Neutrons; Silver
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202113266

In sharp contrast to surface hydrides, reactivities of interstitial hydrides are difficult to explore. When treated with a metal ion (Cu+, Ag+, and Au+), the stable CuI dihydride template [Cu11H2{S2P(OiPr)2}6(C≡CPh)3] (H2Cu11) generates surprisingly three very different compounds, namely [CuH2Cu11{S2P(OiPr)2}6(C≡CPh)3]+ (1), [AgH2Cu14{S2P(OiPr)2}6((C≡CPh)6]+ (2), and [AuCu11{S2P(OiPr)2}6(C≡CPh)3Cl] (3). Compounds 1 and 2 are both MI species and maintain the same number of hydride ligands as their H2Cu11 precursor. Neutron diffraction revealed the first time a trigonal‐pyramidal hydride coordination mode in the AgCu3 environment of 2. 3 has no hydride and exhibits a mixed‐valent [AuCu11]10+ metal core, making it a two‐electron superatom. While the reaction of the [Cu11H2{S2P(OiPr)2}6(C≡CPh)3] template with Cu+ or Ag+ produces Cu12H2 and AgCu14H2 species in which the hydrides behave as Lewis bases, in the reaction with Au+, the hydrides act as reducing agents, leading to a luminescent, two‐electron Au@Cu11 superatom, whose metal core has a defect fcc structure.