化学
炔烃
电子顺磁共振
动力学
拉曼光谱
铜
光谱学
反应机理
吸收光谱法
光化学
结晶学
催化作用
立体化学
核化学
有机化学
核磁共振
光学
物理
量子力学
作者
Ruopeng Bai,Guanghui Zhang,Hong Yi,Zhenwei Wu,Xiaotian Qi,Chao Liu,Jeffrey T. Miller,A. Jeremy Kropf,Emilio E. Bunel,Yu Lan,Aiwen Lei
摘要
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.
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