Nickel complexes of a pincer NN2 ligand:: Multiple carbon-chloride activation of CH2Cl2 and CHCl3 leads to selective carbon-carbon bond formation
Nickel complexes of a pincer NN2 ligand:: Multiple carbon-chloride activation of CH2Cl2 and CHCl3 leads to selective carbon-carbon bond formation
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DOI：
10.1021/ja8025938
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发表时间：
2008-07-02
影响因子：
15
通讯作者：
Hu, Xile
中科院分区：
文献类型：
--
作者：
Csok, Zsolt;Vechorkin, Oleg;Hu, Xile
合成了一种新的钳型双氨基胺配体（NN（2））及其镍、锂配合物，包括镍（II）的甲基、乙基和苯基配合物。Ni（II）烷基络合物与烷基卤化物干净地反应。更有趣的是，Ni（II）烷基与CH（2）Cl（2）和CHCl（3）发生了前所未有的反应，裂解了所有的C-Cl键，并将其替换为C-C键。该反应是高度选择性的，并导致CHCl（2）与烷基格氏试剂的第一次有效的催化偶联。在几分钟内就实现了82%的转化率和47个营业额。CD（2）Cl（2）和1，1-二氯-3，3-二甲基丁烷与（n）BuMgCl的偶联反应也得以实现。初步的机理研究表明，这些反应的自由基引发的过程。
A new pincer-type bis(amino)amine (NN(2)) ligand and its lithium and nickel complexes, including Ni(II) methyl, ethyl, and phenyl complexes, were synthesized. The Ni(II) alkyl complexes react cleanly with alkyl halides. More interestingly, the Ni(II) alkyls undergo unprecedented reactions with CH(2)Cl(2) and CHCl(3) to cleave all the C-Cl bonds and replace them with C-C bonds. The reactions are highly selective and lead to the first efficient catalytic coupling of CHCl(2) with alkyl Grignards. A conversion of 82% and a turnover number of 47 are achieved within minutes. Coupling of CD(2)Cl(2) and 1,1-dichloro-3,3-dimethylbutane with (n)BuMgCl is also realized. Preliminary mechanistic study suggests a radical initiated process for these reactions.