Single-atom copper catalyst for the S-arylation reaction to produce diaryl disulfides

Yiming Zhao; Yan Zhou; Shanshan Lv; Han Li; Qikang Wu; Shaohuan Liu; Wanying Li; Taiyu Chen; Zheng Chen

doi:10.1039/d2sc06738b

Single-atom copper catalyst for the S-arylation reaction to produce diaryl disulfides

Chem Sci. 2023 Mar 29;14(17):4620-4626. doi: 10.1039/d2sc06738b. eCollection 2023 May 3.

Authors

Yiming Zhao¹, Yan Zhou¹, Shanshan Lv¹, Han Li¹, Qikang Wu¹, Shaohuan Liu¹, Wanying Li¹, Taiyu Chen¹, Zheng Chen¹

Affiliation

¹ Key Laboratory of Functional, Ministry of Education, College of Chemistry and Materials Science, Anhui Normal University Wuhu 241000 China chenzh07@mail.ahnu.edu.cn.

Abstract

Single-atom Cu supported on CeO _x nanorod catalysts (Cu₁/CeO _x ) have been synthesized through the anchoring of copper by terminal hydroxyl groups on the CeO _x surface. The oxygen defect characteristics of the CeO _x nanorods promote electron transfer between Cu and CeO _x through a Ce-O-Cu interface, which realizes flexible electronic regulation of the Cu sites. Single-atom Cu species with an oxidation state of between +1 and +2 were formed, which was confirmed by X-ray photoelectron spectroscopy, X-ray fine structure spectroscopy, and electron paramagnetic resonance spectroscopy. Cu₁/CeO _x emerged as a catalyst with advanced catalytic performance for elemental sulfur in S-arylation using aryl iodides, achieving 97.1% iodobenzene conversion and 94.8% selectivity toward diphenyl disulfide. The substituted iodobenzene with different electronic or steric groups successfully realized S-arylation and produced the corresponding diaryl disulfides with high selectivity. The fully exposed single-atom Cu with flexible electronic characteristics successively realized oxidative addition or coordination of multiple substrates, making it possible to obtain diaryl disulfide with high selectivity.