title: Unravelling the hidden link of lithium halides and application in the synthesis of organocuprates.
abstract: As a versatile metal, copper has demonstrated a wide application in acting as both organometallic reagent and catalyst. Organocuprates are among the most used organometallic reagents in the formation of new carbon-carbon bonds in organic synthesis. Therefore, revealing the real structures of organocuprates in solution is crucial to provide insights into the reactivity of organocuprates. Here we provide several important insights into organocuprate chemistry. The main finding contains the following aspects. The Cu(0) particles were detected via the reduction of CuX by nBuLi or PhLi. The Cu(II) precursors CuX2(X=Cl, Br) could be used for the preparation of Gilman reagents. In addition, we provide direct evidence for the role and effect of LiX in organocuprate synthesis. Moreover, the EXAFS spectrum provides direct evidence for the exact structure of Li+CuX2-ate complex in solution. This work not only sheds important light on the role of LiX in the formation of organocuprates but also reports two new routes for organocuprate synthesis.
authors.affiliation: College of Chemistry and Molecular Sciences, The Institute for Advanced Studies (IAS), Wuhan University, Wuhan, Hubei 430072, China.
authors.forename: Hong
authors.initials: H
authors.lastname: Yi
authors.affiliation: College of Chemistry and Molecular Sciences, The Institute for Advanced Studies (IAS), Wuhan University, Wuhan, Hubei 430072, China.
authors.forename: Dali
authors.initials: D
authors.lastname: Yang
authors.affiliation: College of Chemistry and Molecular Sciences, The Institute for Advanced Studies (IAS), Wuhan University, Wuhan, Hubei 430072, China.
authors.forename: Jie
authors.initials: J
authors.lastname: Xin
authors.affiliation: School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400030, China.
authors.forename: Xiaotian
authors.initials: X
authors.lastname: Qi
authors.affiliation: School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400030, China.
authors.forename: Yu
authors.initials: Y
authors.lastname: Lan
authors.affiliation: College of Chemistry and Molecular Sciences, The Institute for Advanced Studies (IAS), Wuhan University, Wuhan, Hubei 430072, China.
authors.forename: Yi
authors.initials: Y
authors.lastname: Deng
authors.affiliation: National Synchrotron Radiation Research Center, Hsinchu 30076, Taiwan.
authors.forename: Chih-Wen
authors.initials: CW
authors.lastname: Pao
authors.affiliation: National Synchrotron Radiation Research Center, Hsinchu 30076, Taiwan.
authors.forename: Jyh-Fu
authors.initials: JF
authors.lastname: Lee
authors.affiliation: College of Chemistry and Molecular Sciences, The Institute for Advanced Studies (IAS), Wuhan University, Wuhan, Hubei 430072, China.|State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China.
authors.forename: Aiwen
authors.initials: A
authors.lastname: Lei