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J Am Chem Soc. 2014 Dec 3;136(48):16760-3. doi: 10.1021/ja5097489. Epub 2014 Nov 20.

Cu(II)-Cu(I) synergistic cooperation to lead the alkyne C-H activation.

Author information

1
College of Chemistry and Molecular Sciences, Wuhan University , Wuhan 430072, P.R. China.

Abstract

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.

PMID:
25383800
DOI:
10.1021/ja5097489
[Indexed for MEDLINE]

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