{bis(tributylphosphine)nickelio}anthracene | 135709-32-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 英文名称: {bis(tributylphosphine)nickelio}anthracene
• 英文别名: anthracene;nickel;tributylphosphane
• CAS: 135709-32-9
• 化学式: C₃₈H₆₄NiP₂
• 分子量: 641.564
• InChiKey: GDWOHWVRUWICNR-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：

  {bis(tributylphosphine)nickelio}anthracene 、 三丁基膦 以 氘代四氢呋喃 为溶剂， 生成 Ni(PBu3)4 、 tris(tri-n-butyl)phosphinonickel(0)
  参考文献：
  名称：

  Synthesis and fluxional behavior of [bis(trialkylphosphine)nickelio]anthracene (alkyl = Et, Bu)

  摘要：

  The title compounds were prepared from the respective (R3P)2NiCl2 complexes and magnesium-anthracene-(THF)3 (or anthracene in the presence of Mg or C8K). The assignment of the anthracene proton NMR signals using NOE in conjunction with magnetization-transfer techniques is described. The complexes undergo haptotropic rearrangements in which the (R3P)2Ni moiety migrates between the two terminal rings of the coordinated anthracene. The rates of these processes are concentration independent and unaffected by the presence of free anthracene and tris(trialkylphosphine)nickel. Kinetic studies in the temperature range -60 to +70-degrees-C using line shape analysis and spin saturation transfer techniques were carried out. It was found that DELTA-H double-ended-dagger = 13.6 kcal mol-1 and DELTA-S double-ended-dagger = -4.3 eu for the haptotropic rearrangement in 2, and similar values were found for 1. Possible mechanisms are discussed. According to H-1, C-13, and P-31 NMR data, the coordination number between the anthracene and the (R3P)2Ni moiety is 4. However, an equilibrium between two eta(2) structures with DELTA-G double-ended-dagger less-than-or-equal-to 4 kcal mol-1 cannot be ruled out.

  DOI：

  10.1021/om00037a054
• 作为产物：
  描述：

  Bogdanovic magnesium 、 [bis(tributylphosphine)nickeldichloride] 以 四氢呋喃 为溶剂， 生成 {bis(tributylphosphine)nickelio}anthracene
  参考文献：
  名称：

  Synthesis and fluxional behavior of [bis(trialkylphosphine)nickelio]anthracene (alkyl = Et, Bu)

  摘要：

  The title compounds were prepared from the respective (R3P)2NiCl2 complexes and magnesium-anthracene-(THF)3 (or anthracene in the presence of Mg or C8K). The assignment of the anthracene proton NMR signals using NOE in conjunction with magnetization-transfer techniques is described. The complexes undergo haptotropic rearrangements in which the (R3P)2Ni moiety migrates between the two terminal rings of the coordinated anthracene. The rates of these processes are concentration independent and unaffected by the presence of free anthracene and tris(trialkylphosphine)nickel. Kinetic studies in the temperature range -60 to +70-degrees-C using line shape analysis and spin saturation transfer techniques were carried out. It was found that DELTA-H double-ended-dagger = 13.6 kcal mol-1 and DELTA-S double-ended-dagger = -4.3 eu for the haptotropic rearrangement in 2, and similar values were found for 1. Possible mechanisms are discussed. According to H-1, C-13, and P-31 NMR data, the coordination number between the anthracene and the (R3P)2Ni moiety is 4. However, an equilibrium between two eta(2) structures with DELTA-G double-ended-dagger less-than-or-equal-to 4 kcal mol-1 cannot be ruled out.

  DOI：

  10.1021/om00037a054

文献信息

• A one-pot method for the preparation of (R3P)2Ni0L complexes
  作者：Amnon Stanger、Anat Shazar

  DOI：10.1016/0022-328x(93)80480-y

  日期：1993.10

  (R3P)2Ni0L complexes is described. The method is based on the reductive elimination of (R3P)2NiMe2 [which is prepared in situ from the corresponding (R3P)2NiCl2 and MeLi] in the presence of a free ligand. The elimination can be induced thermally (at r.t. or higher) or photochemically. A comparison between the thermal and photochemical methods was made with several phosphine-nickel complexes.

  描述了一种新的通用的一锅法制备（R 3 P）2 Ni 0 L配合物。该方法基于（R 3 P）2 NiMe 2 [由相应的（R 3 P）2 NiCl 2和MeLi原位制备]在游离配体存在下的还原消除。消除可以通过热（在室温或更高温度下）或光化学诱导。用几种膦-镍配合物对热和光化学方法进行了比较。