Hydride-doped coinage metal superatoms and their catalytic applications

Superatomic constructs have been identified as a critical component of future technologies. The isolation of coinage metal superatoms relies on partially reducing metallic frameworks to accommodate the mixed valent state required to generate a superatom. Controlling this reduction requires careful consideration in reducing the agent, temperature, and the ligand that directs the self-assembly process. Hydride-based reducing agents dominate the synthetic wet chemical routes to coinage metal clusters. However, within this category, a unique subset of superatoms that retain a hydride/s within the nanocluster post-reduction have emerged. These stable constructs have only recently been characterized in the solid state and have highly unique structural features and properties. The difficulty in identifying the position of hydrides in electron-rich metallic constructs requires the combination and correlation of several analytical methods, including ESI-MS, NMR, SCXRD, and DFT. This text highlights the importance of NMR in detecting hydride environments in these superatomic systems. Added to the complexity of these systems is the dual nature of the hydride, which can act as metallic hydrogen in some cases, resulting in entirely different physical properties. This review includes all hydride-doped superatomic nanoclusters emphasizing synthesis, structure, and catalytic potential. Mixed valent coinage metal clusters can encapsulate different dopants, forming remarkable superatoms while retaining a hydride. In this review, we highlight the hydride's dual nature in the synthesis, structure and application of superatoms.