tris(2-(diisopropylphosphino)phenyl)methane | 1534332-84-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 三苯基化合物
• 英文名称: tris(2-(diisopropylphosphino)phenyl)methane
• 英文别名: [2-[Bis[2-di(propan-2-yl)phosphanylphenyl]methyl]phenyl]-di(propan-2-yl)phosphane；[2-[bis[2-di(propan-2-yl)phosphanylphenyl]methyl]phenyl]-di(propan-2-yl)phosphane
• CAS: 1534332-84-7
• 化学式: C₃₇H₅₅P₃
• 分子量: 592.765
• InChiKey: DBXYONQQQZJQEF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.8
• 重原子数：
  40
• 可旋转键数：
  12
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.51
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  tris(2-(diisopropylphosphino)phenyl)methane 在 sodium amalgam 、 sodium 作用下， 以 乙醚 、 二甲基亚砜 、 甲苯 、 苯 为溶剂， 反应 8.0h， 生成
  参考文献：
  名称：

  Catalytic Reduction of N₂ to NH₃ by an Fe–N₂ Complex Featuring a C-Atom Anchor

  摘要：

  While recent spectroscopic studies have established the presence of an interstitial carbon atom at the center of the iron-molybdenum cofactor (FeMoco) of MoFe-nitrogenase, its role is unknown. We have pursued Fe-N-2 model chemistry to explore a hypothesis whereby this C-atom (previously denoted as a light X-atom) may provide a flexible trans interaction with an Fe center to expose an Fe-N-2 binding site. In this context, we now report on Fe complexes of a new tris(phosphino)alkyl (CP3iPr3) ligand featuring an axial carbon donor. It is established that the iron center in this scaffold binds dinitrogen trans to the C-alkyl-atom anchor in three distinct and structurally characterized oxidation states. Fe-C-alkyl lengthening is observed upon reduction, reflective of significant ionic character in the Fe-C-alkyl interaction. The anionic (CP3iPr3)FeN2- species can be functionalized by a silyl electrophile to generate (CP3iPr3)Fe-N2SiR3. (CP3iPr3)FeN2- also functions as a modest catalyst for the reduction of N-2 to NH3 when supplied with electrons and protons at -78 degrees C under 1 atm N-2 (4.6 equiv NH3/Fe).

  DOI：

  10.1021/ja4114962
• 作为产物：
  描述：

  10-(2-bromophenyl)-10H-dibenzo[b,e]iodininium iodide 在 叔丁基锂 作用下， 以 乙醚 为溶剂， 反应 3.41h， 生成 tris(2-(diisopropylphosphino)phenyl)methane
  参考文献：
  名称：

  Catalytic Reduction of N₂ to NH₃ by an Fe–N₂ Complex Featuring a C-Atom Anchor

  摘要：

  While recent spectroscopic studies have established the presence of an interstitial carbon atom at the center of the iron-molybdenum cofactor (FeMoco) of MoFe-nitrogenase, its role is unknown. We have pursued Fe-N-2 model chemistry to explore a hypothesis whereby this C-atom (previously denoted as a light X-atom) may provide a flexible trans interaction with an Fe center to expose an Fe-N-2 binding site. In this context, we now report on Fe complexes of a new tris(phosphino)alkyl (CP3iPr3) ligand featuring an axial carbon donor. It is established that the iron center in this scaffold binds dinitrogen trans to the C-alkyl-atom anchor in three distinct and structurally characterized oxidation states. Fe-C-alkyl lengthening is observed upon reduction, reflective of significant ionic character in the Fe-C-alkyl interaction. The anionic (CP3iPr3)FeN2- species can be functionalized by a silyl electrophile to generate (CP3iPr3)Fe-N2SiR3. (CP3iPr3)FeN2- also functions as a modest catalyst for the reduction of N-2 to NH3 when supplied with electrons and protons at -78 degrees C under 1 atm N-2 (4.6 equiv NH3/Fe).

  DOI：

  10.1021/ja4114962

文献信息

• Evaluating Molecular Cobalt Complexes for the Conversion of N₂ to NH₃
  作者：Trevor J. Del Castillo、Niklas B. Thompson、Daniel L. M. Suess、Gaël Ung、Jonas C. Peters

  DOI：10.1021/acs.inorgchem.5b00645

  日期：2015.10.5

  Well-defined molecular catalysts for the reduction of N-2 to NH3 with protons and electrons remain very rare despite decades of interest and are currently limited to systems featuring molybdenum or iron. This report details the synthesis of a molecular cobalt complex that generates superstoichiometric yields of NH3 (>200% NH3 per Co-N-2 precursor) via the direct reduction of N-2 with protons and electrons. While the NH3 yields reported herein are modest by comparison to those of previously described iron and molybdenum systems, they intimate that other metals are likely to be viable as molecular N, reduction catalysts. Additionally, a comparison of the featured tris(phosphine)borane Co-N-2 complex with structurally related Co-N-2 and Fe-N-2 species shows how remarkably sensitive the N, reduction performance of potential precatalysts is. These studies enable consideration of the structural and electronic effects that are likely relevant to N-2 conversion activity, including the pi basicity, charge state, and geometric flexibility.
• Catalytic Reduction of N₂ to NH₃ by an Fe–N₂ Complex Featuring a C-Atom Anchor
  作者：Sidney E. Creutz、Jonas C. Peters

  DOI：10.1021/ja4114962

  日期：2014.1.22

  While recent spectroscopic studies have established the presence of an interstitial carbon atom at the center of the iron-molybdenum cofactor (FeMoco) of MoFe-nitrogenase, its role is unknown. We have pursued Fe-N-2 model chemistry to explore a hypothesis whereby this C-atom (previously denoted as a light X-atom) may provide a flexible trans interaction with an Fe center to expose an Fe-N-2 binding site. In this context, we now report on Fe complexes of a new tris(phosphino)alkyl (CP3iPr3) ligand featuring an axial carbon donor. It is established that the iron center in this scaffold binds dinitrogen trans to the C-alkyl-atom anchor in three distinct and structurally characterized oxidation states. Fe-C-alkyl lengthening is observed upon reduction, reflective of significant ionic character in the Fe-C-alkyl interaction. The anionic (CP3iPr3)FeN2- species can be functionalized by a silyl electrophile to generate (CP3iPr3)Fe-N2SiR3. (CP3iPr3)FeN2- also functions as a modest catalyst for the reduction of N-2 to NH3 when supplied with electrons and protons at -78 degrees C under 1 atm N-2 (4.6 equiv NH3/Fe).