文献类型：期刊文献

英文题名：Generation of a Sulfinamide Species from Facile N-O Bond Cleavage of Nitrosobenzene by a Thiolate-Bridged Diiron Complex

作者：Xu, Sunlin[1];Yang, Dawei[1];Wang, Baomin[1];Chen, Yifeng[2,3];Ye, Shengfa[4];Qu, Jingping[1,2]

机构：[1]Dalian Univ Technol, State Key Lab Fine Chem, Dalian 116024, Peoples R China;[2]East China Univ Sci & Technol, State Key Lab Bioreactor Engn, Shanghai Collaborat Innovat Ctr Biomfg, Frontiers Sci Ctr Materiobiol & Dynam Chem, Shanghai 200237, Peoples R China;[3]East China Univ Sci & Technol, Sch Chem & Mol Engn, Shanghai 200237, Peoples R China;[4]Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Catalysis, Dalian 116023, Peoples R China

年份：2021

卷号：143

期号：42

起止页码：17374

外文期刊名：JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

收录：;EI(收录号：20214311058511);WOS:【SCI-EXPANDED(收录号:WOS:000713146100009)】；

基金：This work was supported by the National Natural Science Foundation of China (Nos. 21690064, 22001031), Key Laboratory of Bio-based Chemicals of Liaoning Province of China, and the "111" project of the Ministry of Education of China. We thank Prof. Tao Liu and Dr. Yinshan Meng for providing access to the 57Fe Mossbauer spectrometer.

语种：英文

外文关键词：Iron - Reduction - Aniline - Metal complexes

摘要：The activation of nitrosobenzene promoted by transition-metal complexes has gained considerable interest due to its significance for understanding biological processes and catalytic C-N bond formation processes. Despite intensive studies in the past decades, there are only limited cases where electron-rich metal centers were commonly employed to achieve the N-O or C-N bond cleavage of the coordinated nitrosobenzene. In this regard, it is significant and challenging to construct a suitable functional system for examining its unique reactivity toward reductive activation of nitrosoarene. Herein, we present a {Fe2S2} functional platform that can activate nitrosobenzene via an unprecedented iron-directed thiolate insertion into the N-O bond to selectively generate a well-defined diiron benzenesulfinamide complex. Furthermore, computational studies support a proposal that in this concerted four-electron reduction process of nitrosobenzene the iron center serves as an important electron shuttle. Notably, compared to the intact bridging nitrosoarene ligand, the benzenesulfinamide moiety has priority to convert into aniline in the presence of separate or combined protons and reductants, which may imply the formation of the sulfinamide species accelerates reduction process of nitrosoarene. The reaction pattern presented here represents a novel activation mode of nitrosobenzene realized by a thiolate-bridged diiron complex.