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

Abstract

AbstractIn 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.