Stable and Recyclable Copper Nanoclusters with Exposed Active Sites for Broad‐Scope Protosilylation in Open Air

• Published in: Angewandte Chemie International Edition Vol. 64; no. 4; pp. e202416851 - n/a
• Main Authors: Wen, Songwei, Zhang, Chengkai, Liu, Li‐Juan, Wang, Zhi, Sun, Di, He, Jian
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 21.01.2025; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Alkenes; Catalysis; Chemical reactions; Chemical synthesis; Chemistry; Chemistry, Multidisciplinary; Clusters; Copper; Copper compounds; Ligand Design; Metal Nanoclusters; Nanoclusters; Physical Sciences; Protosilylation; Rare gases; Science & Technology; Sustainable Synthesis; CATALYSIS; ACTIVATION; SILICON; ALLENES; ALKYNES; Sustainable Synthesis; VINYLSILANES; SILYLATION; Protosilylation; SI; Metal Nanoclusters; Copper; Ligand Design; CLUSTER; ACCESS
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202416851

Despite recent advances in cluster‐based catalysis for organic synthesis, the substrate scope of reactions catalyzed by metal nanoclusters is typically not superior to previously established catalytic systems. Herein, we develop new atomically precise copper nanoclusters for protosilylation, with scope expanding to alkenes and simple enynes that were not suitable for prior synthetic methodologies with traditional copper complexes. The involvement of a second copper center in the metal kernel during the migratory insertion step is thought to be responsible for the expanded scope. In addition, the reaction is highly compatible with water and can be carried out in open air rather than under inert gas protection. Mechanistic studies suggest that the cluster‐catalyzed protosilylation proceeds in the absence of silyl radicals. The current findings demonstrate the potential of using metal nanoclusters for practical and sustainable chemical synthesis. The use of maleonitriledithiolate ligands allows for the straightforward synthesis of stable, atomically precise Cu6 nanoclusters with exposed copper active sites in gram scales. These recyclable cluster‐based copper catalysts efficiently promote the protosilylation of C−C multiple bonds under ambient conditions, with a broad substrate scope and high turnover numbers, demonstrating their considerable promise for practical synthetic applications.