Bimetallic Oxidative Addition in Nickel-Catalyzed Alkyl-Aryl Kumada Coupling Reactions

Bimetallic Oxidative Addition in Nickel-Catalyzed Alkyl-Aryl Kumada Coupling Reactions
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DOI:
10.1021/om500506y
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发表时间:
2014-10-27
期刊:
影响因子:
2.8
通讯作者:
Hu, Xile
Hu, Xile
中科院分区:
化学2区
文献类型:
--
作者:
Breitenfeld, Jan;Wodrich, Matthew D.;Hu, Xile

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研究了镍钳形配合物Nickamine催化烷基芳基Kumada偶联反应的机理。使用自由基探针基板和DFT计算的实验建立了一个氧化加成机制。动力学测量表明,transmetalation,而不是氧化加成是营业额决定步骤。金属转移涉及一个β-途径。
The mechanism of alkylaryl Kumada coupling catalyzed by the nickel pincer complex Nickamine was studied. Experiments using radical-probe substrates and DFT calculations established a bimetallic oxidative addition mechanism. Kinetic measurements showed that transmetalation rather than oxidative addition was the turnover-determining step. The transmetalation involved a bimetallic pathway.