A Functionalized Heterogeneous Catalyst from Atomically Precise Pd Au Clusters Facilitates Carbon-Carbon Bond Construction.

It has become possible to establish a connection between homogeneous and heterogeneous catalysis with atomically precise metal clusters. Due to their defined coordination geometry, in this work, atomically precise Pd Au (PPh ) clusters are exploited to identify the crucial factor that can impact the catalytic efficiency for the Suzuki-Miyaura cross-coupling process and further gain valuable insight into the exclusive cooperative effect of the central Pd atom and the peripheral Au atoms of the Pd Au (PPh ) cluster on controlling the cross-coupling reaction. Specifically, a heterogeneous catalyst, namely Pd Au @Resin, is designed by exchanging positively charged Pd Au (PPh ) clusters into the porous resin, thereby not only facilitating catalyst recyclability when performed in a batch reactor, but also realizing time-on-stream performance for the Suzuki-Miyaura cross-coupling reaction carried out in a fixed-bed reactor. The integrated advantages of homogeneous complexes and heterogeneous catalysts are expected to advance the usability of atomically precise metal clusters as heterogeneous catalysts for important bond constructions in homogeneous systems.