[(1,3-bis[(di-tert-butylphosphino)methyl)-4,6-dimethylbenzene(-1H))(CH3)RhCl] | 183996-37-4

• 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: [(1,3-bis[(di-tert-butylphosphino)methyl)-4,6-dimethylbenzene(-1H))(CH3)RhCl]
• 英文别名: Carbanide;chlororhodium(2+);ditert-butyl-[[5-(ditert-butylphosphanylmethyl)-2,4-dimethylbenzene-6-id-1-yl]methyl]phosphane
• CAS: 183996-37-4
• 化学式: C₂₇H₅₀ClP₂Rh
• 分子量: 575.0
• InChiKey: GGNCMHYBKRSVNM-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  10.4
• 重原子数：
  31
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.74
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  [(1,3-bis[(di-tert-butylphosphino)methyl)-4,6-dimethylbenzene(-1H))(CH3)RhCl] 、 silver tetrafluoroborate 以 四氢呋喃 为溶剂， 生成 carbanide;ditert-butyl-[[5-(ditert-butylphosphanylmethyl)-2,4-dimethylbenzene-6-id-1-yl]methyl]phosphane;rhodium(3+);tetrafluoroborate
  参考文献：
  名称：

  Solvent-Controlled Selectivity toward Exclusive C−C or C−H Bond Activation by a Cationic Metal Center

  摘要：

  DOI：

  10.1021/ja990339p
• 作为产物：
  描述：

  di-μ-chloro-bis[bis(cyclo-octene)rhodium] 、 2,4-bis[(di-tert-butylphosphino)methyl]mesitylene 以 苯 为溶剂， 以98%的产率得到[(1,3-bis[(di-tert-butylphosphino)methyl)-4,6-dimethylbenzene(-1H))(CH3)RhCl]
  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

文献信息

• Synthesis, Structure, and Reactivity of Nitrosyl Pincer-Type Rhodium Complexes
  作者：Carina Gaviglio、Yehoshoa Ben-David、Linda J. W. Shimon、Fabio Doctorovich、David Milstein

  DOI：10.1021/om8011536

  日期：2009.3.23

  a linear ↔ bent nitrosyl equilibrium was established, both in solution and in the solid state, between the linear nitrosyl Rh(I) complex 2 and the bent nitrosyl Rh(III) complex [Rh(PCPtBu)(NO)(CO)][BF4] (3). Addition of LiCl to complex 2 resulted in the quantitative formation of the bent nitrosyl complex Rh(PCPtBu)(NO)(Cl) (4). An IR study of solvent interactions of the nitrosyl ligand of complex

  钳型线性亚硝酰基Rh（I）络合物Rh（PCP t Bu）（NO）] [BF 4 ]（2）和[Rh（PCP t BuCH 2）（NO）] [BF 4 ]（8）是报道（PCP t Bu ＝ 1，3-双[（二叔丁基膦基）甲基] -2，4，6-三甲基苯）。配合物2是通过Rh（I）二氮配合物Rh（PCP t Bu）N 2（1）与NOBF 4反应而合成的，同时处理了氯甲烷配合物Rh（PCP t Bu）（CH 3）Cl（7）。使用NOBF 4导致8的形成。添加一氧化碳后，在溶液中和固态下，线性亚硝酰基Rh（I）络合物2和亚硝酰基Rh（III）络合物[Rh（PCP t Bu）（ NO）（CO）] [BF 4 ]（3）。向配合物2中添加LiCl导致定量形成弯曲的亚硝酰基配合物Rh（PCP t Bu）（NO）（Cl）（4）。还提出了对复合物2的亚硝酰基配体在各种溶剂中的溶剂相互作用的IR研究，显示了由溶剂配位
• Metal-Stabilized Methylene Arenium and σ-Arenium Compounds:  Synthesis, Structure, Reactivity, Charge Distribution, and Interconversion
  作者：Arkadi Vigalok、Boris Rybtchinski、Linda J. W. Shimon、Yehoshoa Ben-David、David Milstein

  DOI：10.1021/om980960i

  日期：1999.3.1

  results in clean formation of the new methylene arenium metal complexes ClM[CH2C6H(CH3)2(CH2P(t-Bu)2)2]+OTf- (M = Rh (2a), Ir (4), respectively), which have been fully characterized including an X-ray single-crystal analysis. This new method can be applied to complexes having both electron-donating and electron-withdrawing substituents in the aromatic ring. The methylene arenium complexes bear most of the

  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 =
• Direct Synthesis of Thermally Stable PCP-Type Rhodium Carbenes
  作者：Arkadi Vigalok、David Milstein

  DOI：10.1021/om990764r

  日期：2000.5.1

  Dinitrogen rhodium(I) complexes with bis-chelating diphosphine ligands are shown to be robust precursors toward Rh carbene complexes. While the Rh aryl Nz complex 1 reacts with phenyldiazomethane, giving the phenylcarbene complex, the Rh alkyl Nz precursor 3 reacts with 2 equiv of phenyldiazomethane to yield the Rh vinyl carbene complex 5. The more stable diphenyldiazomethane does not form carbene complexes under similar conditions, giving instead the stable diazomethane complex 10.