[(2,6-bis(2,6-dimethylphenyliminoethyl)pyridine)CoBr] | 1253376-49-6

• 英文名称: [(2,6-bis(2,6-dimethylphenyliminoethyl)pyridine)CoBr]
• 英文别名: [Co(2,6-bis(2,6-dimethylphenyliminoethyl)pyridine)Br]
• CAS: 1253376-49-6
• 化学式: C₂₅H₂₇BrCoN₃
• 分子量: 508.407
• InChiKey: VBOLLZYMAPQICK-RYIWROBHSA-M

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 氢给体数：
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反应信息

• 作为产物：
  描述：

  1-溴-2,4,6-三叔丁基苯 、 [(2,6-bis(2,6-dimethylphenyliminoethyl)pyridine)Co(N2)] 以 氘代苯 为溶剂， 生成 [(2,6-bis(2,6-dimethylphenyliminoethyl)pyridine)CoBr] 、 [(2,6-bis(2,6-dimethylphenyliminoethyl)pyridine)Co(C6H2-2,4,6-(t-Bu)3)]
  参考文献：
  名称：

  Binuclear Oxidative Addition of Aryl Halides

  摘要：

  Reaction of LCoCH2SiMe3(L= 2,6-bis[2,6-dimethyl-phenyliminoethyl]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 LCoCl2 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.

  DOI：

  10.1021/om100811f

文献信息

• Radical Mechanisms in the Reaction of Organic Halides with Diiminepyridine Cobalt Complexes
  作者：Di Zhu、Ilia Korobkov、Peter H. M. Budzelaar

  DOI：10.1021/om300182c

  日期：2012.5.28

  LCo(N2) reacts with many alkyl and aryl halides RX, including aryl chlorides, to give a mixture of LCoR and LCoX in a halogen atom abstraction mechanism. Intermediacy of free alkyl and aryl radicals is confirmed by the ring-opening of cyclopropylmethyl to crotyl, and the rearrangement of 2,4,6-tBu3C6H2 to 3,5-tBu2C6H3CMe2CH2, before binding to Co. The organocobalt species generated in this way react further

  可以通过Na / Hg还原LCoCl 2或氢解LCoCH 2 SiMe 3来制备形式上为Co（0）的配合物LCo（N 2）（L = 2,6-双（2,6-二甲基苯基亚氨基乙基）吡啶）。在后一反应中，LCOH可以通过与N≡CC反应被截留6 ħ 4 -4-CL，得到LCoN═CHC 6 ħ 4 -4-CL。LCo（N 2）与许多烷基和芳基卤化物RX（包括芳基氯化物）反应，在卤素原子提取机理中得到LCoR和LCoX的混合物。游离烷基和芳基的中间体通过环丙基甲基对巴豆基的开环和2,4,6- t Bu的重排得到证实3 C 6 H 2至3,5- t Bu 2 C 6 H 3 CMe 2 CH 2，然后与Co结合。以这种方式生成的有机钴物质进一步与活化的卤化物R'X（烷基碘；烯丙基和苄基卤化物）反应）以最有可能再次是卤素提取机理的方式产生交叉偶联产物RR'。DFT研究支持为这两个步骤建议的基本途径。MeI与LCoCH