Selective Hydroperoxygenation of Olefins Realized by a Coinage Multimetallic 1‐Nanometer Catalyst

Abstract

The science of particles on a sub-nanometer (ca. 1 nm) scale has attracted worldwide attention. However, it has remained unexplored because of the technical difficulty in the precise synthesis of sub-nanoparticles (SNPs). We recently developed the "atom-hybridization method (AHM)" for the precise synthesis of SNPs by using a suitably designed macromolecule as a template. We have now investigated the chemical reactivity of alloy SNPs obtained by the AHM. Focusing on the coinage metal elements, we systematically evaluated the oxidation reaction of an olefin catalyzed by these SNPs. The SNPs showed high catalytic performance even under milder conditions than those used with conventional catalysts. Additionally, the hybridization of multiple elements enhanced the turnover frequency and the selectivity for the formation of the hydroperoxide derivative. We discuss the unique quantum-sized catalysts providing generally unstable hydroperoxides from the viewpoint of the miniaturization and hybridization of materials.

Highly Accurate Synthesis of Quasi‐sub‐nanoparticles by Dendron‐assembled Supramolecular Templates

“…Subsequently, by chemical reduction of these complexes, SNPs with fine-controlled atomicity can be obtained. [30][31][32][33] However, even this macromolecular technique is unsuitable for the synthesis of QSNPs because the costs involved in synthesizing higher-generation dendrimers tend to increase exponentially due to a significant decline in yields and purities caused by steric hindrance. The available number of imine units in DPAs was up to 60 and large DPAs including more than 60 imines have not been synthesized.…”