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Binuclear oxidative addition of aryl halides

机译:芳基卤化物的双核氧化加成

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摘要

Reaction of LCoCH_2SiMe_3 (L = 2,6-bis[2,6- dimethylphenyliminoethyl]pyridine) with H_2 produces LCo(N _2), presumably via intermediate LCoH. Reaction of LCo(N_2) (prepared in this way or via reaction of LCoCl_2 with Na/Hg) with aryl halides ArX (X = Cl, Br, I) produces LCoAr and LCoX in a ratio depending on the nature of Ar and X. For X = Cl, the reaction is slowest but also produces the largest amount of LCoAr. Electron-withdrawing substituents both accelerate the reaction and improve the yield of LCoAr. Computational studies support a radical mechanism for this reaction, involving displacement of N_2 to give LCo(XAr) followed by loss of the Ar radical, which then binds to a second Co(0) moiety.
机译:LCoCH_2SiMe_3(L = 2,6-双[2,6-二甲基苯基亚氨基乙基]吡啶)与H_2的反应产生LCo(N _2),大概是通过中间体LCoH。 LCo(N_2)(以这种方式或通过LCoCl_2与Na / Hg的反应制备)与卤代芳基ArX(X = Cl,Br,I)的反应生成LCoAr和LCoX的比例取决于Ar和X的性质。对于X = Cl,反应最慢,但也产生最大量的LCoAr。吸电子取代基既加快了反应速度,又提高了LCoAr的收率。计算研究支持该反应的自由基机理,包括置换N_2生成LCo(XAr),然后失去Ar自由基,然后Ar自由基与第二个Co(0)部分结合。

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