Selective Hydroperoxygenation of Olefin Realized by Coinage Multimetallic 1-nanometer Catalyst.

The science of particles on a sub-nanometer (~ 1 nm) scale has attracted worldwide attention. However, this field of science has remained unexplored because of the technical difficulty in the precise synthesis of sub-nanoparticles (SNPs). Thus, we recently developed the 'atom-hybridization method (AHM)' that precisely synthesizes the SNPs by using a suitably-designed macromolecule as a template. In this study, toward revealing this unexplored field, we newly investigated the chemical reactivity of alloy SNPs obtained by the AHM. Focusing on the coinage metal elements, the oxidation reaction of an olefin catalyzed by these SNPs was systematically evaluated. The SNPs showed a high catalytic performance even under the milder condition in contrast to conventional catalysts. Additionally, the hybridization of multiple elements enhanced the turnover frequency and the selectivity of the hydroperoxide derivative. We discuss the unique quantum-sized catalysts providing generally unstable hydroperoxides from the viewpoint of miniaturization and hybridization of the materials.