Neutral Five-Coordinate Arylated Copper(Ⅲ) Complex: Key Intermediate in Copper-Mediated Arene Trifluoromethylation  

作　　者：Guangyu Wang Man Li Xuebing Leng Xiaosong Xue Qilong Shen 

机构地区：[1]Key Laboratory of Organofluorine Chemistry,Shanghai Institute of Organic Chemistry,University of Chinese Academy of Sciences,Chinese Academy of Sciences,345 Lingling Lu,Shanghai,200032 China [2]Key Laboratory of Material Chemistry for Energy Conversion and Storage,Ministry of Education,Hubei Key Laboratory of Bioinorganic Chemistry and Materia Medica,Hubei Key Laboratory of Materials Chemistry and Service Failure,School of Chemistry and Chemical Engineering,Huazhong Universityof Scienceand Technology,Wuhan,Hubei 430074,China

出　　处：《Chinese Journal of Chemistry》2022年第16期1924-1930,共7页中国化学（英文版）

基　　金：the financial support from the National Key Research and Development Program of China(No.2021YFF0701700);the National Natural Science Foundation of China(Nos.21625206,22061160465,22122104,21933004 and 22103027).

摘　　要：Five-coordinate neutral Cu(Ⅲ)complexes have long been considered as the key intermediates in copper-mediated/catalyzed arene trifluoromethylative reactions,but the identity of these complexes remains elusive.Herein,we reported,for the first time,the preparation and characterization of these putative complexes[(bpy)Cu(CF_(3))_(2)(C_(6)F_(4)R)]and investigation of their C(sp^(2))-CF_(3) bond-forming reductive elimination.Our mechanistic studies including kinetic studies,the effect of temperature and solvents,the effect of the para-substitution of the ligand as well as DFT calculations suggest that C(sp^(2))-CF_(3) reductive elimination process proceeds via synchronous bond-breaking/bond-forming process.

关 键 词：Cu(Ⅲ) Reductive elimination TRIFLUOROMETHYL Mechanism Concerted pathway 

分 类 号：O62[理学—有机化学]