[Cu(NPh2)2][Li(1,10-phenanthroline)3] | 1256086-70-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹啉及其衍生物
• 英文名称: [Cu(NPh2)2][Li(1,10-phenanthroline)3]
• 英文别名: [Cu(NPh2)2][Li(phen)3]
• CAS: 1256086-70-0
• 化学式: C₂₄H₂₀CuN₂*C₃₆H₂₄LiN₆
• 分子量: 947.55
• InChiKey: XIBYLXVIMDJUBK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  4-碘甲苯 、 [Cu(NPh2)2][Li(1,10-phenanthroline)3] 以 二甲基亚砜 为溶剂， 生成 copper(l) iodide
  参考文献：
  名称：

  Cu(I)−Amido Complexes in the Ullmann Reaction: Reactions of Cu(I)−Amido Complexes with Iodoarenes with and without Autocatalysis by CuI

  摘要：

  A series of Cu(I)-amido complexes both lacking ancillary ligands and containing 1,10-phenanthroline (phen) as ancillary ligand have been prepared. These complexes react with iodoarenes to form arylamine products, and this reactivity is consistent with the intermediacy of such complexes in catalytic Ullmann amination reactions. The stoichiometric reactions of the Cu(I)-amido complexes with iodoarenes are autocatalytic, with the free Cul generated during the reaction serving as the catalyst. Such autocatalytic behavior was not observed for reactions of iodoarenes with copper(I) amidates, imidates, or phenoxides. The selectivity of these complexes for two sterically distinct aryl halides under various conditions imply that the autocatalytic reaction proceeds by forming highly reactive [CuNPh2](n) lacking phen. Reactions with radical probes imply that the reactions of phen-ligated Cu(I)-amido complexes with iodoarenes occur without the intermediacy of aryl radicals. Density functional theory calculations on the oxidative addition of iodoarenes to Cu(I) species are consistent with faster reactions of iodoarenes with CuNPh2 species lacking phen in DMSO than reactions of iodoarenes with LCuNPh2 in which L = phen. The free-energy barrier computed for the reaction of Phl with (DMSO)CuNPh2 was 21.8 kcal/mol, while that for the reaction of Phl with (phen)CuNPh2 was 33.4 kcal/mol.

  DOI：

  10.1021/ja105695s
• 作为产物：
  描述：

  1,10-菲罗啉 、 [Cu(NPh2)2][Cu(1,10-phenanthroline)2] 、 lithium diphenylamide 以 四氢呋喃 为溶剂， 以92%的产率得到[Cu(NPh2)2][Li(1,10-phenanthroline)3]
  参考文献：
  名称：

  Cu(I)−Amido Complexes in the Ullmann Reaction: Reactions of Cu(I)−Amido Complexes with Iodoarenes with and without Autocatalysis by CuI

  摘要：

  A series of Cu(I)-amido complexes both lacking ancillary ligands and containing 1,10-phenanthroline (phen) as ancillary ligand have been prepared. These complexes react with iodoarenes to form arylamine products, and this reactivity is consistent with the intermediacy of such complexes in catalytic Ullmann amination reactions. The stoichiometric reactions of the Cu(I)-amido complexes with iodoarenes are autocatalytic, with the free Cul generated during the reaction serving as the catalyst. Such autocatalytic behavior was not observed for reactions of iodoarenes with copper(I) amidates, imidates, or phenoxides. The selectivity of these complexes for two sterically distinct aryl halides under various conditions imply that the autocatalytic reaction proceeds by forming highly reactive [CuNPh2](n) lacking phen. Reactions with radical probes imply that the reactions of phen-ligated Cu(I)-amido complexes with iodoarenes occur without the intermediacy of aryl radicals. Density functional theory calculations on the oxidative addition of iodoarenes to Cu(I) species are consistent with faster reactions of iodoarenes with CuNPh2 species lacking phen in DMSO than reactions of iodoarenes with LCuNPh2 in which L = phen. The free-energy barrier computed for the reaction of Phl with (DMSO)CuNPh2 was 21.8 kcal/mol, while that for the reaction of Phl with (phen)CuNPh2 was 33.4 kcal/mol.

  DOI：

  10.1021/ja105695s