A low-nuclear Ag<sub>4</sub> nanocluster as a customized catalyst for the cyclization of propargylamine with CO<sub>2</sub>.

Li, Lin; Lv, Ying; Sheng, Hongting; Du, Yonglei; Li, Haifeng; Yun, Yapei; Zhang, Ziyi; Yu, Haizhu et al. · Nat Commun · 2023

basic_science · Level V

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Abstract

The preparation of 2-Oxazolidinones using CO<sub>2</sub> offers opportunities for green chemistry, but multi-site activation is difficult for most catalysts. Here, A low-nuclear Ag<sub>4</sub> catalytic system is successfully customized, which solves the simultaneous activation of acetylene (-C≡C) and amino (-NH-) and realizes the cyclization of propargylamine with CO<sub>2</sub> under mild conditions. As expected, the Turnover Number (TON) and Turnover Frequency (TOF) values of the Ag<sub>4</sub> nanocluster (NC) are higher than most of reported catalysts. The Ag<sub>4</sub>* NC intermediates are isolated and confirmed their structures by Electrospray ionization (ESI) and <sup>1</sup>H Nuclear Magnetic Resonance (<sup>1</sup>H NMR). Additionally, the key role of multiple Ag atoms revealed the feasibility and importance of low-nuclear catalysts at the atomic level, confirming the reaction pathways that are inaccessible to the Ag single-atom catalyst and Ag<sub>2</sub> NC. Importantly, the nanocomposite achieves multiple recoveries and gram scale product acquisition. These results provide guidance for the design of more efficient and targeted catalytic materials.