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首页> 外文期刊>Chemistry: A European journal >Ligand versus Complex: C-F and C-H Bond Activation of Polyfluoroaromatics at a Cyclic (Alkyl)(Amino)Carbene
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Ligand versus Complex: C-F and C-H Bond Activation of Polyfluoroaromatics at a Cyclic (Alkyl)(Amino)Carbene

机译：配体与复合物：C-F和C-H键活化在环状（烷基）（氨基）卡宾酸盐中的多氟芳烃

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摘要

C-F and C-H bond activation reactions of polyfluoroaromatics at the cyclic (alkyl)(amino)carbene (cAAC) cAAC~(methyl) (1) are reported. Studies on the C-F bond activation using the cAAC-stabilized nickel(0) complex [Ni(cAAC~(methyl))_2] (2) have shown that 2 does not react with fluorinated arenes. However, these investigations led to the observation of C-F bond cleavage of perfluorinated arenes by the carbene ligand cAAC~(methyl) (1) itself. The reaction of 1 with C_6F_6, C_6F_5-C_6F_5, C_6F_5-CF_3, and C_5F_5N afforded the insertion products of cAAC into one of the C-F bonds of the substrate, that is, the C-F bond activation products (cAAC~(methyl))F(Ar~f) (Ar~f=C_6F_5 4a, C_6F_4-C_6F_5 4b, C_6F_4-CF_3 4c, C_5F_4N 4d). These products decompose readily upon heating to 80°C within a few hours in solution with formation of ionic iminium salts [(cAAC~(methyl))(Arf)][X] 6a-d or neutral alkenyl perfluoroaryl imine compounds 7a-d. The compounds (cAAC~(methyl))F(Ar~f) 4a-d readily transfer fluoride, which has been exemplified by the fluoride transfer of all compounds using BF_3 etherate as fluoride acceptor. Fluoride transfer has also been achieved starting from (cAAC~(methyl))F(C_6F_4-CF_3) (4c) or (cAAC~(methyl))F(C_5F_4N) (4d) to other selected substrates such as trimethylchlorosilane, benzoyl chloride and tosyl chloride. Instead of C-F bond activation, insertion of the cAAC into the C-H bond was observed if 1 was treated with the partially fluorinated arenes C_6F_5H, 1,2,4,5-C_6F_4H_2, 1,3,5-C_6F_3H_3, and 1,3-C_6F_2H_4. The compounds (cAAC~(methyl))H(Ar~f) (Ar~f=C_6F_5 12e, 2,3,5,6-C_6F_4H 12 f, 2,4,6-C_6F_3H_2 12g and 2,6-C_6F_2H_3 12h) have been isolated in good yields and have been characterized including X-ray analysis. Fluorobenzene C_6FH_5 (pK_a ≈37), the least C-H acidic fluoroarene used in this study, does not react. In order to investigate the scope and limitations of this type of cAAC C-H bond activation reaction, cAAC~(methyl) (1) was treated with several
机译：报道了环状（烷基）（氨基）卡宾（CAAC）CAAC〜（甲基）（1）在环状（烷基）（氨基）甲苯（CAAC）CAAC〜（甲基）（1）时的C-F和C-H键活化反应。使用Caac稳定镍（0）复合物的C-F键活化的研究[Ni（Caac〜（甲基））_ 2]（2）表明2不与氟化芳烃反应。然而，这些研究导致了通过Carbene配体Caac〜（1）本身的全氟化芳烃的C-F键切割的观察。用C_6F_6，C_6F_5-C_6F_5，C_6F_5-CF_3和C_5F_5N的反应得到CAAC的插入产物，进入基材的CF键之一，即CF键活化产物（CAAC〜（甲基））F（ AR〜F）（AR〜F = C_6F_5 4A，C_6F_4-C_6F_5 4B，C_6F_4-CF_3 4C，C_5F_4N 4D）。这些产品在溶液中加热至80℃时，在溶液中加热至80℃，形成离子氨基鎓盐[（Caac〜（甲基））（ARF）] [x] 6a-d或中性链烯基全氟芳基亚胺化合物7a-d。化合物（Caac〜（甲基））F（Ar〜F）4a-d容易转移氟化物，其通过使用BF_3醚酯作为氟化物受体的所有化合物的氟化物转移所示。从（CAAC〜（甲基））F（C_6F_4-CF_3）（4C）或（CAAC〜（甲基））F（C_5F_4N）（4D）至其它选定的基材如三甲基氯硅烷，苯甲酰基和氯化氯烷。如果用部分氟化的芳烃处理1，则观察到将Caac插入CH键的CAAC进入CH键，1,2,5-C_6F_3H_2,1,3,5-C_6F_3H_3和1,3- c_6f_2h_4。化合物（Caac〜（甲基））H（Ar〜F）（Ar〜F = C_6F_5 12E，2,3,5,6-C_6F_4H 12 F，2,4,6-C_6F_3H_2 12G和2,6-C_6F_2H_3 12H ）已以良好的产量分离，并且已经表征包括X射线分析。氟苯C_6FH_5（PK_A≈37），本研究中使用的最少的C-H酸性氟甲烯不反应。为了探讨这种Caac C-H键活化反应的范围和限制，用几种Caac〜（甲基）（1）处理

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