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In Situ Monitoring of Transmetallation in Electric Potential-Promoted Oxidative Coupling in a Single-Molecule Junction    

文献类型:期刊文献

中文题名:In Situ Monitoring of Transmetallation in Electric Potential-Promoted Oxidative Coupling in a Single-Molecule Junction

作者:Yunpeng Li[1];Chengxi Zhao[1];Rui Wang[1];Ajun Tang[1];Wenjing Hong[2];Dahui Qu[1];He Tian[1];Hongxiang Li[1]

机构:[1]Key Laboratory for Advanced Materials,Feringa Nobel Prize Scientist Joint Research Center,Frontiers Science Center for Materiobiology and Dynamic Chemistry,Institute of Fine Chemicals,School of Chemistry and Molecular Engineering,East China University of Science and Technology,Shanghai 200237;[2]Key Laboratory of Physical Chemistry of Solid Surfaces,College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005

年份:2023

卷号:5

期号:1

起止页码:191

中文期刊名:CCS Chemistry

外文期刊名:中国化学会会刊(英文)

收录:Scopus;CSCD:【CSCD2023_2024】;

基金:This work was supported by the National Natural Science Foundation of China(grant nos.21875279,21790362,and 22075080);the Shanghai Municipal Science and Technology Major Project(grant no.2018SHZDZX03);the Fundamental Research Funds for the Central Universities,the Programme of Introducing Talents of Discipline to Universities(grant no.B16017);the Program of Shanghai Academic/Technology Research Leader(grant no.19XD1421100).

语种:英文

中文关键词:single-molecule junction;transmetallation;oxidative coupling;molecular electronics;in situ detection

摘要:To monitor and investigate chemical reactions in real time and in situ is a long-standing,challenging goal in chemistry.Herein,an electric potential-promoted oxidative coupling reaction of organoboron compounds without the addition of base is reported,and the transmetallation process involved is monitored in real time and in situ with the scanning tunneling microscopy break single-molecule junctions(STMBJ)technique.We found that the electric potential applied determined the transmetallation.At low-bias voltage,the first-step transmetallation process occurred and afforded Au─C-bonded aryl gold intermediates.The electronic properties of organoboron compounds have a strong influence on the transmetallation process,and electron-rich compounds facilitate this transformation.At high-bias voltage,the second-step transmetallation process took place,and the corresponding intermediate(highly reactive diaryl metal complex)was detected with the assistance of Pd(OAc)_(2).Our work demonstrates the applications of STMBJ on in situ monitoring and catalyzing of chemical reactions and provides a new methodology to fabricate singlemolecule devices.

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