Stabilizing Few‐Atom Platinum Clusters by Zinc Single‐Atom‐Glue for Efficient Anti‐Markovnikov Alkene Hydrosilylation

Few-atom metal clusters (FAMCs) exhibit superior performance in catalyzing complex molecular transformations due to their special spatial environments and electronic states, compared to single-atom catalysts (SACs). However, achieving the efficient and accurate synthesis of FAMCs while avoiding the formation of other species, such as nanoparticles and SACs, still remains challenges. Herein, we report a two-step strategy for synthesis of few-atom platinum (Pt) clusters by predeposition of zinc single-atom-glue (Zn₁) on MgO nanosheets (Pt_n-Zn₁/MgO), where FAMCs can be obtained over a wide range of Pt contents (0.09 to 1.45 wt %). Zn atoms can act as Lewis acidic sites to allow electron transfer between Zn and Pt through bridging O atoms, which play a crucial role in the formation and stabilization of few-atom Pt clusters. Pt_n-Zn₁/MgO exhibited a high selectivity of 93 % for anti-Markovnikov alkene hydrosilylation. Moreover, an excellent activity with a turnover frequency of up to 1.6×10⁴ h^-1 can be achieved, exceeding most of the reported Pt SACs. Further theoretical studies revealed that the Pt atoms in Pt_n-Zn₁/MgO possess moderate steric hindrance, which enables high selectivity and activity for hydrosilylation. This work presents some guidelines for utilizing atomic-scale species to increase the synthesis efficiency and precision of FAMCs.