Cu(II)鈥揅u(I) Synergistic Cooperation to Lead the Alkyne C鈥揌 Activation

详细信息    查看全文

• 作者：Ruopeng Bai ; Guanghui Zhang ; Hong Yi ; Zhiliang Huang ; Xiaotian Qi ; Chao Liu ; Jeffrey T. Miller ; A. Jeremy Kropf ; Emilio E. Bunel ; Yu Lan ; Aiwen Lei
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：December 3, 2014
• 年：2014
• 卷：136
• 期：48
• 页码：16760-16763
• 全文大小：281K
• ISSN：1520-5126

文摘

An efficient alkyne C鈥揌 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鈥揌 activation step. Kinetics study showed Cu(II) plays a role as oxidant in C鈥揅 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)鈥揅u(II) synergistic cooperation procedure is proposed for the reaction.