Heptanuclear Silver Hydride Clusters as Catalytic Precursors for the Reduction of 4-Nitrophenol

We report on the design, synthesis, and characterization of the first silver hydride clusters solely protected and stabilized by dithiophosphonate ligands and their application for the in situ generation of silver nanoparticles towards the catalytic reduction of 4-nitrophenol in an aqueous system. The synthesis of the silver monohydride cluster involves the incorporation of an interstitial hydride using sodium borohydride. Poly-nuclear magnetic resonance and mass spectrometry were used to establish the structural properties. The structural properties were then confirmed with a single-crystal X-ray diffraction analysis, which showed a distorted tetracapped tetrahedron core with one hydride ion encapsulated within the core of the silver framework. Additionally, the synthesized heptanuclear silver hydride was utilized as a precursor for the in situ generation of silver nanoparticles, which simultaneously catalyzed the reduction of 4-nitrophenol. The mechanism of the catalytic activity was investigated by first synthesizing AgNPs, which was subsequently used as a catalyst. The kinetic study showed that the pseudo-first constant obtained using the cluster (2.43 × 10^-2 s^-1) was higher than that obtained using the synthesized AgNPs (2.43 × 10^-2 s^-1). This indicated that the silver monohydride cluster was more active owing to the release of the encapsulated hydride ion and greater reaction surface prior to aggregation.