Locating Interstitial Hydrides in MH₂@Cu₁₄ (M = Cu, Ag) Clusters by Single-Crystal X-ray Diffraction

Abstract

Two structures, [Cu15H2(S2CN n Bu2)6(CCPh)6][CuCl2] (1) and [AgH2Cu14{S2P(O i Pr)2}6(CCPh)6][PF6] (2), are characterized by X-ray crystallography with high-quality single crystals. The position of interstitial hydrides can be accurately located. In addition, the refinement of the hydrides with anisotropic displacement parameters (ADPs) was successful. The distances between the central atom and copper atoms, as well as the distances within the metal cages surrounding the hydrides, are analyzed and compared with similar MH2@Cu14 (M = Cu, Ag, Pd) compounds. This work provides a thoughtful and accurate assessment of the considerations and challenges associated with anisotropic refinement for H atoms, particularly in X-ray data collection.

Hydride-doped coinage metal superatoms and their catalytic applications

“…In both instances, the compact nature of the hydride allows it to occupy interstitial sites, which can be challenging to identify experimentally, given the proximity to heavy metals. 12,13 This text summarizes the unique coupling effects and invaluable information on hydride environments seen in these constructs via nuclear magnetic resonance (NMR).…”

The structure–activity relationship of copper hydride nanoclusters in hydrogenation and reduction reactions

“… 24 Locating these hydride ligands using XRD poses challenges due to the weak diffraction of hydrogen. 25 The advancement of neutron diffraction has facilitated the identification and location of hydrides in copper NCs. 26 Consequently, it was discovered that many copper NCs are in fact copper hydride NCs.…”