Tetrahedral Mg3M Clusters: A New Class of Superatom Catalysts for the Suzuki-Miyaura Reaction.

Abstract

Exploring low-cost and high-activity cluster catalysts for the Suzuki-Miyaura (SM) reaction based on the intriguing superatom concept is of great interest. To achieve this goal, a series of Mg₃M (M = Sc-Zn) clusters have been obtained via the rational design and random search in this study. The superatom identities of these Mg₃M clusters are guaranteed by their compact tetrahedral structures, high stability, and superatomic configurations. The performance of these Mg₃M superatoms in adsorbing benzene halides as well as catalyzing the oxidative addition, transmetalation, and reductive elimination steps of the SM reaction was evaluated step by step to screen out feasible catalysts for the SM reaction. Finally, Mg₃Ni was selected as the best superatom catalyst for the SM reaction among these Mg₃M superatoms in view of its low rate-limiting energy barrier of 24.94 kcal/mol, which is even lower than that of 26.35 kcal/mol for Mg₃Pd. Moreover, the catalytic performance of Mg₃Ni deposited on a graphitic carbon nitride (g-C₃N₄) in the rate-limiting step of the SM reaction was assessed to confirm the practical application of this superatom in the catalysis of the SM reaction. This study not only provides cheap replacement catalysts of noble metals for SM reaction, but also intrigues researchers' interests to further extend the practical application of superatom clusters in catalyzing other C-C coupling reactions.