Cu(II)-Cu(I) Synergistic Cooperation to Lead the Alkyne C-H Activation
Cu(II)-Cu(I) Synergistic Cooperation to Lead the Alkyne C-H Activation
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Cu(II)-Cu(I)协同作用引导炔烃C-H活化
DOI：
10.1021/ja5097489
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发表时间：
2014-12-03
影响因子：
15
通讯作者：
Lei, Aiwen
中科院分区：
文献类型：
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作者：
Bai, Ruopeng;Zhang, Guanghui;Lei, Aiwen
一个有效的炔C-H活化和homocoupling程序已被研究表明，Cu（II）/Cu（I）的协同合作可能涉及。原位拉曼光谱研究了动力学行为，得出的结论是，铜（I），而不是铜（II）参与的速率决定步骤。IR、EPR和X-射线吸收光谱提供了结构信息，表明在C-H活化步骤中，Cu（I）比Cu（II）与炔具有更强的相互作用。动力学研究表明，Cu（II）在C-C键的形成过程中起氧化剂的作用，这是反应的一个快速步骤。X-波段EPR谱表明CuCl_2（TMEDA）的配位环境受Cu（I）的影响。提出了Cu（I）-Cu（II）协同作用机理。
An efficient alkyne C-H activation and homocoupling procedure has been studied which indicates that a Cu(II)/Cu(I) synergistic cooperation might be involved. In situ Raman spectroscopy was employed to study kinetic behavior, drawing the conclusion that Cu(I) rather than Cu(II) participates in the rate-determining step. IR, EPR, and X-ray absorption spectroscopy evidence were provided for structural information, indicating that Cu(I) has a stronger interaction with alkyne than Cu(II) in the C-H activation step. Kinetics study showed Cu(II) plays a role as oxidant in C-C bond construction step, which was a fast step in the reaction. X-band EPR spectroscopy showed that the coordination environment of CuCl2(TMEDA) was affected by Cu(I). A putative mechanism with Cu(I)-Cu(II) synergistic cooperation procedure is proposed for the reaction.