H3[DPPN3N] | 1232366-58-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: H3[DPPN3N]
• 英文别名: (3,5-(2,5-diisopropylpyrrolyl)C6H3NHCH2CH2)3N；N',N'-bis[2-[3,5-bis[2,5-di(propan-2-yl)pyrrol-1-yl]anilino]ethyl]-N-[3,5-bis[2,5-di(propan-2-yl)pyrrol-1-yl]phenyl]ethane-1,2-diamine
• CAS: 1232366-58-3
• 化学式: C₈₄H₁₂₀N₁₀
• 分子量: 1269.94
• InChiKey: TZFUSWJVPUHXAU-UHFFFAOYSA-N

物化性质

• 密度：
  1.06±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  21.6
• 重原子数：
  94
• 可旋转键数：
  30
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  68.9
• 氢给体数：
  3
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  tetrachlorobis(tetrahydrofurano)molybdenum(IV) 、 H3[DPPN3N] 在 LiN(Si(CH₃)3)2 作用下， 以 tetrahydrofuran 为溶剂， 以57%的产率得到Mo(IV)Cl((3,5-(2,5-diisopropylpyrrolyl)C6H3NCH2CH2)3N)
  参考文献：
  名称：

  Synthesis of [(DPPNCH₂CH₂)₃N]³⁻ Molybdenum Complexes (DPP = 3,5-(2,5-Diisopropylpyrrolyl)₂C₆H₃) and Studies Relevant to Catalytic Reduction of Dinitrogen

  摘要：

  Molybdenum complexes that contain a new TREN-based ligand [(3,5-(2,5-diisopropylpyrrolyl)(2)C6H3NCH2CH2)(3)N](3-) ([DPPN3N](3-)) that are relevant to the catalytic reduction of dinitrogen have been prepared. They are [Bu4N]{[DPPN3N]MoN2), [DPPN3N]MoN2, [DPPN3N]MON=NH, {[DPPN3N]MoN=NH2)[BArt4], [DPPN3N]Mo N, {[DPPN3N]Mo NH}[BAr4f], and {[DPPN3N]MoNH3}[BAr4f] NMR and IR data for [Bu4N]{[DPPN3N]MoN2} and [DPPN3N]MoN2 are close to those reported for the analogous [HIPTN3N](3) compounds (HIPT = hexaisopropylterphenyl), which suggests that the degree of reduction of dinitrogen is virtually identical in the two systems. However, X-ray studies and several exchange studies support the conclusion that the apical pocket is less protected in [DPPN3N]Mo complexes than in [HIPTN3N]Mo complexes. For example, N-15/N-14 exchange studies showed that exchange in [DPPN3N]MoN2 is relatively facile (t(1/2) approximate to 1 h at 1 atm) and depends upon dinitrogen pressure, in contrast to the exchange in [HIPTN3N]MoN2. Several of the [DPPN3N]Mo complexes, e.g., the [DPPN3N]MoN2 and [DPPN3N]MoNH3 species, are also less stable in solution than the analogous "parent" [HIPTN3N]Mo complexes. Four attempted catalytic reductions of dinitrogen with [DPPN3N]MoN yielded 2.53 +/- 0.35 equiv of total ammonia. These studies reveal more than any other just how sensitive a successful catalytic reduction is to small changes in the triamidoamine supporting ligand.

  DOI：

  10.1021/ja1008213
• 作为产物：
  描述：

  三(2-氨基乙基)胺 、 DPPBr 在 tris-(dibenzylideneacetone)dipalladium(0) 、 R-(+)-1,1'-联萘-2,2'-双二苯膦 、 sodium t-butanolate 作用下， 以 甲苯 为溶剂， 反应 24.0h， 以74%的产率得到H3[DPPN3N]
  参考文献：
  名称：

  Synthesis of [(DPPNCH₂CH₂)₃N]³⁻ Molybdenum Complexes (DPP = 3,5-(2,5-Diisopropylpyrrolyl)₂C₆H₃) and Studies Relevant to Catalytic Reduction of Dinitrogen

  摘要：

  Molybdenum complexes that contain a new TREN-based ligand [(3,5-(2,5-diisopropylpyrrolyl)(2)C6H3NCH2CH2)(3)N](3-) ([DPPN3N](3-)) that are relevant to the catalytic reduction of dinitrogen have been prepared. They are [Bu4N]{[DPPN3N]MoN2), [DPPN3N]MoN2, [DPPN3N]MON=NH, {[DPPN3N]MoN=NH2)[BArt4], [DPPN3N]Mo N, {[DPPN3N]Mo NH}[BAr4f], and {[DPPN3N]MoNH3}[BAr4f] NMR and IR data for [Bu4N]{[DPPN3N]MoN2} and [DPPN3N]MoN2 are close to those reported for the analogous [HIPTN3N](3) compounds (HIPT = hexaisopropylterphenyl), which suggests that the degree of reduction of dinitrogen is virtually identical in the two systems. However, X-ray studies and several exchange studies support the conclusion that the apical pocket is less protected in [DPPN3N]Mo complexes than in [HIPTN3N]Mo complexes. For example, N-15/N-14 exchange studies showed that exchange in [DPPN3N]MoN2 is relatively facile (t(1/2) approximate to 1 h at 1 atm) and depends upon dinitrogen pressure, in contrast to the exchange in [HIPTN3N]MoN2. Several of the [DPPN3N]Mo complexes, e.g., the [DPPN3N]MoN2 and [DPPN3N]MoNH3 species, are also less stable in solution than the analogous "parent" [HIPTN3N]Mo complexes. Four attempted catalytic reductions of dinitrogen with [DPPN3N]MoN yielded 2.53 +/- 0.35 equiv of total ammonia. These studies reveal more than any other just how sensitive a successful catalytic reduction is to small changes in the triamidoamine supporting ligand.

  DOI：

  10.1021/ja1008213

文献信息

• Synthesis of [(DPPNCH₂CH₂)₃N]³⁻ Molybdenum Complexes (DPP = 3,5-(2,5-Diisopropylpyrrolyl)₂C₆H₃) and Studies Relevant to Catalytic Reduction of Dinitrogen
  作者：Michael R. Reithofer、Richard R. Schrock、Peter Müller

  DOI：10.1021/ja1008213

  日期：2010.6.23

  Molybdenum complexes that contain a new TREN-based ligand [(3,5-(2,5-diisopropylpyrrolyl)(2)C6H3NCH2CH2)(3)N](3-) ([DPPN3N](3-)) that are relevant to the catalytic reduction of dinitrogen have been prepared. They are [Bu4N][DPPN3N]MoN2), [DPPN3N]MoN2, [DPPN3N]MON=NH, [DPPN3N]MoN=NH2)[BArt4], [DPPN3N]Mo N, [DPPN3N]Mo NH}[BAr4f], and [DPPN3N]MoNH3}[BAr4f] NMR and IR data for [Bu4N][DPPN3N]MoN2} and [DPPN3N]MoN2 are close to those reported for the analogous [HIPTN3N](3) compounds (HIPT = hexaisopropylterphenyl), which suggests that the degree of reduction of dinitrogen is virtually identical in the two systems. However, X-ray studies and several exchange studies support the conclusion that the apical pocket is less protected in [DPPN3N]Mo complexes than in [HIPTN3N]Mo complexes. For example, N-15/N-14 exchange studies showed that exchange in [DPPN3N]MoN2 is relatively facile (t(1/2) approximate to 1 h at 1 atm) and depends upon dinitrogen pressure, in contrast to the exchange in [HIPTN3N]MoN2. Several of the [DPPN3N]Mo complexes, e.g., the [DPPN3N]MoN2 and [DPPN3N]MoNH3 species, are also less stable in solution than the analogous "parent" [HIPTN3N]Mo complexes. Four attempted catalytic reductions of dinitrogen with [DPPN3N]MoN yielded 2.53 +/- 0.35 equiv of total ammonia. These studies reveal more than any other just how sensitive a successful catalytic reduction is to small changes in the triamidoamine supporting ligand.