[N(o-C6H4P(i)Pr2)2]NiH | 918339-41-0

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: [N(o-C6H4P(i)Pr2)2]NiH
• 英文别名: [(i)Pr-PNP]NiH
• CAS: 918339-41-0
• 化学式: C₂₄H₃₇NNiP₂
• 分子量: 460.202
• InChiKey: NOJAMDADYTUQQZ-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：

  [N(o-C6H4P(i)Pr2)2]NiH 、 苯 在 Al(CH₃)3 作用下， 以 苯 为溶剂， 生成 [N(o-C6H4P(i)Pr2)2]NiPh
  参考文献：
  名称：

  Intermolecular Arene C−H Activation by Nickel(II)

  摘要：

  Intermolecular arene C-H activation mediated by a divalent nickel species under extremely mild conditions is described. The reactions of either Ni(COD)2 with H[N(o-C6H4PR2)2] (H[R-PNP]; R = iPr, Cy) in benzene at room temperature or [R-PNP]NiCl with LiBHEt3 in THF at -35 degrees C produced the corresponding [R-PNP]NiH in high yield. Addition of 1 equiv of B(C6F5)3 to a benzene solution of [R-PNP]NiH at room temperature led to the formation of a mixture that contains [R-PNP]NiPh and [R-PNP]Ni(C6F5), both of which are proposed to evolve from zwitterionic [R-PNP]Ni(mu-H)B(C6F5)3. In contrast, the reaction of [R-PNP]NiH with AlMe3 in benzene at room temperature afforded exclusively the corresponding [R-PNP]NiPh. Similar results were also observed for intermolecular toluene and m-xylene C-H activation by [R-PNP]NiH. A parallel study involving [R-PNP]NiMe (R = Ph, iPr, Cy) on the reactivity of intermolecular arene activation reveals the significance of pi basicity of Ni(II) in these molecules. The remarkable reactivity of inexpensive Ni(II) species established in this study is attractive, particularly from an economic viewpoint, as compared to the current alternatives of 4d and 5d metals.

  DOI：

  10.1021/ja065505p
• 作为产物：
  描述：

  bis(1,5-cyclooctadiene)nickel (0) 、 bis(2-diisopropylphosphinophenyl)amine 以 苯 为溶剂， 生成 [N(o-C6H4P(i)Pr2)2]NiH
  参考文献：
  名称：

  Intermolecular Arene C−H Activation by Nickel(II)

  摘要：

  Intermolecular arene C-H activation mediated by a divalent nickel species under extremely mild conditions is described. The reactions of either Ni(COD)2 with H[N(o-C6H4PR2)2] (H[R-PNP]; R = iPr, Cy) in benzene at room temperature or [R-PNP]NiCl with LiBHEt3 in THF at -35 degrees C produced the corresponding [R-PNP]NiH in high yield. Addition of 1 equiv of B(C6F5)3 to a benzene solution of [R-PNP]NiH at room temperature led to the formation of a mixture that contains [R-PNP]NiPh and [R-PNP]Ni(C6F5), both of which are proposed to evolve from zwitterionic [R-PNP]Ni(mu-H)B(C6F5)3. In contrast, the reaction of [R-PNP]NiH with AlMe3 in benzene at room temperature afforded exclusively the corresponding [R-PNP]NiPh. Similar results were also observed for intermolecular toluene and m-xylene C-H activation by [R-PNP]NiH. A parallel study involving [R-PNP]NiMe (R = Ph, iPr, Cy) on the reactivity of intermolecular arene activation reveals the significance of pi basicity of Ni(II) in these molecules. The remarkable reactivity of inexpensive Ni(II) species established in this study is attractive, particularly from an economic viewpoint, as compared to the current alternatives of 4d and 5d metals.

  DOI：

  10.1021/ja065505p

文献信息

• Divergent Carbonylation Reactivity Preferences of Nickel Complexes Containing Amido Pincer Ligands: Migratory Insertion versus Reductive Elimination
  作者：Lan-Chang Liang、Yu-Ting Hung、Yu-Lun Huang、Pin-Shu Chien、Pei-Ying Lee、Wei-Chen Chen

  DOI：10.1021/om201041z

  日期：2012.1.23

  The reactivity of a series of nickel(II) hydride, alkyl, and anilide complexes supported by amido diphosphine ligands, including symmetrical [N(o-C6H4PR2)2]− (R = Ph (1a), iPr (1c), Cy (1d)) and unsymmetrical [N(o-C6H4PPh2)(o-C6H4PiPr2)]− (1b), with carbon monoxide is described. Exposure of a benzene solution of [1a–d]NiH to carbon monoxide under ambient conditions leads to reductive elimination of

  酰胺基二膦配体（包括对称的[N（o -C 6 H 4 PR 2）2 ] - ] （R = Ph（1a），i Pr （1c），Cy（1d））和非对称[N（o -C 6 H 4 PPh 2）（o -C 6 H 4 P i Pr 2）] -（1b），用一氧化碳进行描述。在环境条件下，将[ 1a – d ] NiH的苯溶液暴露于一氧化碳会导致二芳基胺的还原消除，从而给出定量为零价的二羰基镍复合物[H· 1a – d ] Ni（CO）2（2）。将CO迁移到[ 1 ] NiR在苯溶液中的Ni-R键中可得到Ni（II）-酰基衍生物[ 1 ] NiC（O）R（R = Me（3），Et（4），n-己基（5），2-降冰片基（6））。有趣的是，酰基3a和由于C–N键形成的还原性消除作用，图4a生成[RC（O）N（o -C 6 H 4 PPh 2）2 ] Ni（CO）2（R = Me（7a），Et（8a））而在相似条件下，3b