carbanide;chloroiridium(2+);ditert-butyl-[[5-(ditert-butylphosphanylmethyl)-2,4-dimethylbenzene-6-id-1-yl]methyl]phosphane | 183996-45-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: carbanide;chloroiridium(2+);ditert-butyl-[[5-(ditert-butylphosphanylmethyl)-2,4-dimethylbenzene-6-id-1-yl]methyl]phosphane
• CAS: 183996-45-4
• 化学式: C₂₇H₅₀ClIrP₂
• 分子量: 664.315
• InChiKey: INMPBHABJIQWSI-UHFFFAOYSA-M

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：

  carbanide;chloroiridium(2+);ditert-butyl-[[5-(ditert-butylphosphanylmethyl)-2,4-dimethylbenzene-6-id-1-yl]methyl]phosphane 、 氘代三氟甲磺酸 以 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  金属稳定的亚甲基亚芳基和σ-Arenium化合物：合成，结构，反应性，电荷分布和互变

  摘要：

  通式为ClM（CH 3）[C 6 H（CH 3）2（CH 2 P（t-Bu）2）2 ]（M = Rh（1），Ir（3））的铑和铱配合物的质子化强酸（HOTf，三氟甲磺酸）导致完全形成新亚甲基arenium金属的配合物CLM [CH 2 ç 6 H（CH 3）2（CH 2 P（叔丁基）2）2 ] +光学传递函数-（M = Rh（2a），Ir（4）），这些特征已得到充分表征，包括X射线单晶分析。该新方法可以应用于在芳环中既具有给电子取代基又具有吸电子取代基的配合物。亚甲基芳烃配合物在环中带有大部分正电荷，从而导致其较高的CH酸度。这些配合物与NEt 3的去质子化反应生成了新的金属亚二甲苯配合物12（M = Rh）和13（M = Ir），可以通过与HOTf反应转化为亚甲基芳烃配合物。该阳离子配合物的反应-光学传递函数+的Rh（R）[C 6 H（CH 3）2（CH 2 P（叔丁基）2）2 ]（R =

  DOI：

  10.1021/om980960i
• 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)-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