(tpa^Mes)V(tetrahydrofuran) | 1265529-54-1

• 分子结构分类: 有机化合物
• 英文名称: (tpa^Mes)V(tetrahydrofuran)
• 英文别名: (tpa^Mes)V(THF)
• CAS: 1265529-54-1
• 化学式: C₄₆H₅₃N₄OV
• 分子量: 728.895
• InChiKey: GRWRKSUJYXQDGF-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：

  一氧化二氮 、 (tpa^Mes)V(tetrahydrofuran) 以 甲苯 为溶剂， 生成 V(N(CH2C4H2NMes)3)(nitrous oxide-N)
  参考文献：
  名称：

  A Structurally Characterized Nitrous Oxide Complex of Vanadium

  摘要：

  Nitrous oxide (N2O), a widespread greenhouse gas, is a thermodynamically potent and environmentally green oxidant that is an attractive target for activation by metal centers. However, N2O remains underutilized owing to its high kinetic stability, and the poor ligand properties of this molecule have made well-characterized metal-N2O complexes a rarity. We now report a vanadium-pyrrolide system that reversibly binds N2O at room temperature and provide the first single-crystal X-ray structure of such a complex. Further characterization by vibrational spectroscopy and DFT calculations strongly favor assignment as a linear, N-bound metal-N2O complex.

  DOI：

  10.1021/ja110798w
• 作为产物：
  描述：

  [VCl3(thf)3] 、 tris((5-(2,4,6-trimethylphenyl)-1H-pyrrol-2-yl)methyl)amine 在 C₄H₉Li 作用下， 以 乙醚 为溶剂， 以70%的产率得到(tpa^Mes)V(tetrahydrofuran)
  参考文献：
  名称：

  A Structurally Characterized Nitrous Oxide Complex of Vanadium

  摘要：

  Nitrous oxide (N2O), a widespread greenhouse gas, is a thermodynamically potent and environmentally green oxidant that is an attractive target for activation by metal centers. However, N2O remains underutilized owing to its high kinetic stability, and the poor ligand properties of this molecule have made well-characterized metal-N2O complexes a rarity. We now report a vanadium-pyrrolide system that reversibly binds N2O at room temperature and provide the first single-crystal X-ray structure of such a complex. Further characterization by vibrational spectroscopy and DFT calculations strongly favor assignment as a linear, N-bound metal-N2O complex.

  DOI：

  10.1021/ja110798w

文献信息

• Well-Defined Vanadium Organoazide Complexes and Their Conversion to Terminal Vanadium Imides: Structural Snapshots and Evidence for a Nitrene Capture Mechanism
  作者：W. Hill Harman、Michael F. Lichterman、Nicholas A. Piro、Christopher J. Chang

  DOI：10.1021/ic301673g

  日期：2012.9.17

  We report the synthesis and structural characterization of a family of well-defined organoazide complexes supported by a three-fold-symmetric pyrrolide scaffold and their conversion to the corresponding terminal imido congeners. Kinetic measurements on a series of structurally homologous but electronically distinct vanadium organoazide complexes reveal that the azido-to-imido transformations proceed via a process that is first-order in the metal complex and has a positive entropy of activation. Further studies suggest that these reactions may involve metal-mediated generation and capture of nitrene fragments.