carbanide;chloroiridium(2+);ditert-butyl-[[5-(ditert-butylphosphanylmethyl)-3-methoxy-2,4-dimethylbenzene-6-id-1-yl]methyl]phosphane | 183996-47-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: carbanide;chloroiridium(2+);ditert-butyl-[[5-(ditert-butylphosphanylmethyl)-3-methoxy-2,4-dimethylbenzene-6-id-1-yl]methyl]phosphane
• CAS: 183996-47-6
• 化学式: C₂₈H₅₂ClIrOP₂
• 分子量: 694.341
• InChiKey: DQFREAOPTPMMNN-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  10.41
• 重原子数：
  33
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  以 氘代苯 为溶剂， 以99%的产率得到carbanide;chloroiridium(2+);ditert-butyl-[[5-(ditert-butylphosphanylmethyl)-3-methoxy-2,4-dimethylbenzene-6-id-1-yl]methyl]phosphane
  参考文献：
  名称：

  A Room Temperature Direct Metal Insertion into a Nonstrained Carbon−Carbon Bond in Solution. C−C vs C−H Bond Activation

  摘要：

  The diphosphine 1,3-bis[(di-tert-butylphosphino)methyl]-2,4,6-trimethylbenzene (la) upon reacting with the rhodium and iridium olefin complexes M(2)(olefin)(4)Cl-2 (M = Rh, Ir) undergoes rapid, selective metal insertion into the strong unstrained aryl-methyl bond under very mild conditions (room temperature), yielding CIM(CH3)-[C6H(CH3)(2)(CH2P(t-Bu)(2))(2)] (M = Rh (4a), Ir (7a)). The carbon-carbon bond activation is competitive with a parallel C-H activation process, which results in formation of complexes ClMH(L)[CH2C6H(CH3)(2)(CH2P(t-Bu)(2))(2)] (M = Rh (3a), Ir (6a); L = cyclooctene inthe case of 6a and is absent in 3a). Complexes 3a and 6a undergo facile C-H reductive elimination (at room temperature (3a) or upon moderate heating (6a)), followed by C-C oxidative addition, resulting in clean formation of 4a and 7a, respectively. The C-C bond activation products are stable under the reaction conditions, demonstrating that this process is the thermodynamically favorable one. X-ray single-crystal analysis of 4a demonstrates that the rhodium atom is located in the center of a square pyramid, with the methyl group occupying the position trans to the vacant coordination site. Direct kinetic comparison of the C-C and C-H activation processes shows that-in contrast to theoretical calculations-metal insertion into the carbon-carbon bond in this system is not only thermodynamically but also kinetically preferred over the competing insertion into the carbon-hydrogen bond. When the Ligand 1,3-bis[(di-tert-butylphosphino)methyl]-2,4, (Ib), bearing the strong electron-donating methoxy group in the position trans to the Ar-CH3 bond to be cleaved, was used instead of la, no effect on the reaction rate or on the ratio between the C-H and C-C activation products was observed. Our observations indicate that the C-C oxidative addition proceeds via a three-centered mechanism involving a nonpolar transition state, similar to the one proposed for C-H activation of hydrocarbons. An eta(2)-arene complex is not involved in the C-C activation process.

  DOI：

  10.1021/ja962253r