[3-[Di(propan-2-yl)-sulfidophosphaniumyl]-2-methylphenyl]-di(propan-2-yl)-sulfidophosphanium | 1353655-96-5

• 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: [3-[Di(propan-2-yl)-sulfidophosphaniumyl]-2-methylphenyl]-di(propan-2-yl)-sulfidophosphanium
• 英文别名: [3-[di(propan-2-yl)-sulfidophosphaniumyl]-2-methylphenyl]-di(propan-2-yl)-sulfidophosphanium
• CAS: 1353655-96-5
• 化学式: C₁₉H₃₄P₂S₂
• 分子量: 388.558
• InChiKey: LHHYHQRRSBOVTG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  23
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  2
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  [Rh(COE)2(acetone)2]BF4 、 [3-[Di(propan-2-yl)-sulfidophosphaniumyl]-2-methylphenyl]-di(propan-2-yl)-sulfidophosphanium 以 丙酮 为溶剂， 以90.4%的产率得到[Ru(CH3)(acetone)(C6H3(PS(CH(CH3)2)2)2)]BF4
  参考文献：
  名称：

  Exclusive C–C Oxidative Addition in a Rhodium Thiophosphoryl Pincer Complex and Computational Evidence for an η³-C–C–H Agostic Intermediate

  摘要：

  The room-temperature reaction between the Rh(I) precursor [Rh(COE)(2)(acetone)(2)]BF4 (COE = cyclooctene) and a new thiophosphoryl-based SCS pincer ligand leads to oxidative addition of an sp(2)-sp(3) C-C bond as the only observed outcome, despite the presence of accessible sp(3) C-H bonds. A DFT study reveals that the chemistry of the SCS system is controlled by pi repulsion between occupied rhodium d orbitals and the lone-pair electrons on the two sulfur atoms. This repulsion gives rise to the thermodynamic selectivity for C-C over C-H cleavage, as it is attributed to the higher electronegativity of a methyl versus hydride ligand, thereby allowing more effective release of excessive pi electron density. It is also demonstrated that the observed C-C and unobserved C-H cleavage pathways originate from a common intermediate that features a novel eta(3)-C-C-H agostic interaction. The COE ligand is shown to play an important role by greatly stabilizing this intermediate, making it the only available entry point to both reaction pathways.

  DOI：

  10.1021/om201205y
• 作为产物：
  描述：

  2,6-bis(diisopropylphosphino)toluene 在 sulfur 作用下， 以 四氢呋喃 为溶剂， 反应 21.0h， 以97.7%的产率得到[3-[Di(propan-2-yl)-sulfidophosphaniumyl]-2-methylphenyl]-di(propan-2-yl)-sulfidophosphanium
  参考文献：
  名称：

  Exclusive C–C Oxidative Addition in a Rhodium Thiophosphoryl Pincer Complex and Computational Evidence for an η³-C–C–H Agostic Intermediate

  摘要：

  The room-temperature reaction between the Rh(I) precursor [Rh(COE)(2)(acetone)(2)]BF4 (COE = cyclooctene) and a new thiophosphoryl-based SCS pincer ligand leads to oxidative addition of an sp(2)-sp(3) C-C bond as the only observed outcome, despite the presence of accessible sp(3) C-H bonds. A DFT study reveals that the chemistry of the SCS system is controlled by pi repulsion between occupied rhodium d orbitals and the lone-pair electrons on the two sulfur atoms. This repulsion gives rise to the thermodynamic selectivity for C-C over C-H cleavage, as it is attributed to the higher electronegativity of a methyl versus hydride ligand, thereby allowing more effective release of excessive pi electron density. It is also demonstrated that the observed C-C and unobserved C-H cleavage pathways originate from a common intermediate that features a novel eta(3)-C-C-H agostic interaction. The COE ligand is shown to play an important role by greatly stabilizing this intermediate, making it the only available entry point to both reaction pathways.

  DOI：

  10.1021/om201205y

文献信息

• Exclusive C–C Oxidative Addition in a Rhodium Thiophosphoryl Pincer Complex and Computational Evidence for an η³-C–C–H Agostic Intermediate
  作者：Michael Montag、Irena Efremenko、Yael Diskin-Posner、Yehoshoa Ben-David、Jan M. L. Martin、David Milstein

  DOI：10.1021/om201205y

  日期：2012.1.9

  The room-temperature reaction between the Rh(I) precursor [Rh(COE)(2)(acetone)(2)]BF4 (COE = cyclooctene) and a new thiophosphoryl-based SCS pincer ligand leads to oxidative addition of an sp(2)-sp(3) C-C bond as the only observed outcome, despite the presence of accessible sp(3) C-H bonds. A DFT study reveals that the chemistry of the SCS system is controlled by pi repulsion between occupied rhodium d orbitals and the lone-pair electrons on the two sulfur atoms. This repulsion gives rise to the thermodynamic selectivity for C-C over C-H cleavage, as it is attributed to the higher electronegativity of a methyl versus hydride ligand, thereby allowing more effective release of excessive pi electron density. It is also demonstrated that the observed C-C and unobserved C-H cleavage pathways originate from a common intermediate that features a novel eta(3)-C-C-H agostic interaction. The COE ligand is shown to play an important role by greatly stabilizing this intermediate, making it the only available entry point to both reaction pathways.