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

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 Cu-I dihydride template [Cu11H2{S2P((OPr)-Pr-i)(2)}(6)(C CPh)(3)] (H2Cu11) generates surprisingly three very different compounds, namely [CuH2Cu11{S2P((OPr)-Pr-i)(2)}(6)(C CPh)(3)](+) (1), [AgH2Cu14{S2P((OPr)-Pr-i)(2)}(6)((C CPh)(6)](+) (2), and [AuCu11{S2P((OPr)-Pr-i)(2)}(6)(C CPh)(3)Cl] (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 trigonalpyramidal 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.

Automated summary

The reactivities of interstitial hydrides are difficult to explore compared to surface hydrides. By treating with metal ions, the stable Cu-I dihydride template can generate three very different compounds, including the first appearance of a trigonal pyramidal hydride coordination mode in compound 2.