The Role of Oxidation during the Synthesis of Silver‐Glutathione Monolayer‐Protected Clusters

The synthesis of metal monolayer‐protected clusters (MPCs) is still not well understood. It was recently shown that the mechanism of MPC formation involves sequential growth, wherein small MPCs form first and then grow into progressively larger sizes. The sequential growth model does not entirely explain all experimental observations, however. For example, the evolution of MPC product sizes is found to be a non‐monotonic function of reaction kinetics, whereas the sequential growth model predicts monotonic behavior. Size evolution of MPCs is studied during synthetic reactions for a wide range of kinetics and it is found that all syntheses began with the sequential growth of MPCs but also found that growth transitioned to degradation if reduction kinetics are fast enough to give way to ambient oxidation. It is identified that MPCs can degrade via oxidation during syntheses and in a manner that is opposite to sequential growth, namely by forming smaller known MPC species from larger MPC species. This sequential degradation process therefore played an important role in determining final MPC products for reactions with fast reduction kinetics. Together, complementary oxidative and reductive processes provide a more complete description of MPC synthesis as well as new tools for controlling metal MPC synthesis. Oxidation plays an important role in determining the product distribution of silver monolayer‐protected cluster syntheses. Oxidation reactions involving ambient oxygen and free glutathione ligands can shift the product distributions toward smaller sizes, but via different mechanisms. Understanding the interplay between competing reductive and oxidative reactions should improve the ability to design syntheses, particularly those targeting specific clusters.