The catalytic performance of (ZrO)n (n = 1–4, 12) clusters for Suzuki–Miyaura cross-coupling: a DFT study

Superatoms are special clusters with similar physicochemical properties to individual atoms in the periodic table, which open up new avenues for exploring inexpensive catalysts. Given that the ZrO superatom possesses the same number of valence electrons as a Pd atom, the mechanisms of the Suzuki–Miyaura reaction catalyzed by (ZrO)_n (n = 1–4) clusters have been investigated and compared with the corresponding Pd_n (n = 1–4) species to explore superatom-based catalysts for the formation of C–C bonds via a density functional theory (DFT) study. It was interesting to find that the catalytic activities of (ZrO)_n (n = 1–4) towards the Suzuki–Miyaura reaction gradually improved as the cluster size increased. Therefore, to obtain more efficient catalysts, the catalytic activity of a well-designed (ZrO)₁₂ nanocage towards this cross-coupling reaction has been further evaluated. Gratifyingly, this nanocage shows excellent catalytic performance for the considered coupling reaction, which is even comparable to that of the commonly used Pd catalyst and outperforms the corresponding Pd₁₂ cluster. We hope this study can not only provide valuable guidance for the development of noble metal-like catalysts for C–C bond formation, but also expand the application of superatoms in the catalysis of organic reactions.