(tetrakis(2,4,6-triisopropylphenyl)porphyrinato)rhodium(II)*carbon monoxide | 138856-88-9

• 英文名称: (tetrakis(2,4,6-triisopropylphenyl)porphyrinato)rhodium(II)*carbon monoxide
• CAS: 138856-88-9
• 化学式: C₈₁H₁₀₀N₄ORh
• 分子量: 1248.62
• InChiKey: JDBSDKKAOQDQFF-ZJKSSAIJSA-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

• 作为产物：
  描述：

  (tetrakis(2,4,6-triisopropylphenyl)porphyrinato)rhodium(II) 在 一氧化碳 作用下， 以 甲苯 为溶剂， 生成 (tetrakis(2,4,6-triisopropylphenyl)porphyrinato)rhodium(II)*carbon monoxide
  参考文献：
  名称：

  Formation and reactivity of (tetraarylporphyrinato)rhodium(II) monocarbonyls: bent RhIICO complexes that react like acyl radicals

  摘要：

  Reactions for a series of rhodium(II) porphyrins with CO are used in illustrating the use of ligand steric effects in both promoting and inhibiting CO coupling to form alpha-diketone complexes ((por)RhC(O)C(O)Rh(por)). [Tetrakis(2,4,6-trimethylphenyl)porphyrinato]rhodium(II), (TMP)Rh., reacts with CO to produce an equilibrium between a C-C-bonded diamagnetic dimer (TMP)RhC(O)C(O)Rh(TMP), with a small amount of a paramagnetic (S = 1/2) monomer, (TMP)RhCO, but only the monocarbonyl complex is observed for the most sterically demanding porphyrin complex examined: [tetrakis(2,4,6-triisopropylphenyl)porphyrinato]rhodium(II), (TTiPP)Rh.. EPR spectra for ((TMP)RhCO)-C-13 and ((TTiPP)RhCO)-C-13 display three distinct g transitions which indicate the presence of nonlinear RhCO units. (TMP)RhCO reacts like an acyl radical, as evidenced by dimerization through C-C bonding to form (TMP)RhC(O)C(O)Rh(TMP), reactions with (Bu)3SnH and H-2 that produce the formyl complex (TMP)RhCHO, and reaction with styrene to form (TMP)RhC(O)CH2CH(C6H5)C(O)Rh(TMP). Thermodynamic and activation parameters for the dimerization of (TMP)RhCO through C-C bonding provides an enthalpy profile for the carbon monoxide coupling reaction.

  DOI：

  10.1021/ja00031a022

文献信息

• Equilibrium thermodynamic studies for the formation of 1:1 complexes of CO and ethene with a rhodium(II) porphyrin metallo-radical
  作者：Leah Basickes、Andrew G Bunn、Bradford B Wayland

  DOI：10.1139/v01-052

  日期：2001.5.1

  Tetra(2,4,6 triisopropropyl phenyl)porphyrinatorhodium(II) ((TTiPP)Rh II ·1) is a persistent metal-centered radi - cal with the odd electron in the rhodium(II) dz 2 orbital. (TTiPP)Rh II · forms 1:1 complexes with CO and CH2CH2 where the porphyrin ligand steric properties inhibit further reactions of the one-electron activated substrates. 1 H NMR para- magnetic shifts at a series of temperatures are

  四(2,4,6 三异丙基苯基)卟啉铑(II) ((TTiPP)Rh II ·1) 是一种持久的金属中心基团，在铑(II) dz 2 轨道上有奇数电子。(TTiPP)Rh II · 与 CO 和 CH2CH2 形成 1:1 复合物，其中卟啉配体的空间特性抑制单电子活化底物的进一步反应。在一系列温度下的 1 H NMR 顺磁位移用于评估与 1 形成 ((TTiPP)Rh II (CO))·2 (ΔH° = -5.5 ± 0.5 kcal mol -1) 的 CO 配合物的热力学; ΔS°=- 9 ±1c al K -1 mol -1 )。相关的 1 H NMR 研究表明，1 与乙烯的键合不如 CO。