[HRh(CO)3(tris(2,4-di-tert-butylphenyl)phosphite)] | 850093-87-7

• 英文名称: [HRh(CO)3(tris(2,4-di-tert-butylphenyl)phosphite)]
• 英文别名: [HRh(CO)3(P(O-2,4-(t-Bu)2-Ph)3)]
• CAS: 850093-87-7
• 化学式: C₄₅H₆₄O₆PRh
• 分子量: 834.879
• InChiKey: MVRYACXETZLNMQ-UHFFFAOYSA-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：

  dodecacarbonyltetrarhodium(0) 、 抗氧剂168 、 氢气 在 CO 作用下， 以 氘代甲苯 为溶剂， 生成 [HRh(CO)3(tris(2,4-di-tert-butylphenyl)phosphite)] 、 [HRh(CO)2(tris(2,4-di-tert-butylphenyl)phosphite)2]
  参考文献：
  名称：

  在庞大的单亚磷酸酯配体存在下氢化铑的形成：光谱和固态研究。

  摘要：

  已经研究了用大体积的三（2,4-二叔丁基苯基）亚磷酸酯P（Obtbp）（3）改性铑催化剂的预成型。对苯二酚型前体配合物[Rh（TropBr（3））（CO）{P（Obtbp）（3）}]。P（Obtbp）（3）.CH（3）COCH（3）的X射线晶体结构测定）（TropBr（3）= 3,5,7-tribromotropolonate）和游离的P（Obtbp）（3）配体被报道。对特定的亚磷酸铑修饰的催化剂及其前体进行的系统原位IR和NMR研究已鉴定出两种不同的氢化铑。{（1）H，（31）P} HMBC NMR实验使在加氢甲酰化条件下观察到的（31）P NMR光谱清晰可见。该物种被标识为[HRh（CO）（3）{P（Obtbp）（3）}]和[HRh（CO）（2）{P（Obtbp）（3）}（2）]。

  DOI：

  10.1039/b416917d

文献信息

• Synthesis and characterisation of two novel Rh(I) carbene complexes: Crystal structure of [Rh(acac)(CO)(L1)]
  作者：Michael S. Datt、Jerald J. Nair、Stefanus Otto

  DOI：10.1016/j.jorganchem.2005.04.046

  日期：2005.7

  The [Rh(acac)(CO)(L)] (acac = acetylacetonato; L-1 = 1,3-bis-(2,6-diisopropylphenyl)imidazolinylidene and L-2 = 1,3-bis-(2,4,6-trimethylphenyl)imidazolinylidene) complexes were prepared by the action of the parent carbene on [Rh(acac)(CO)(2)] in THF. The crystal structure characterisation of [Rh(acac)(CO)(L-1)] revealed a slightly distorted square planar geometry with the carbene ligand orientated almost perpendicular to the equatorial plane; an elongated trans Rh-O bond of 2.0806(18) angstrom reflecting the considerable trans-influence of the carbene ligand. By measuring the CO stretching frequencies in a range of [Rh(acac)(CO)(L)] complexes (L = CO, L-1, L-2, PPh3, P"Bu-3, P(O-2,4-Bu-t(2)-Ph)(3)) the following electron donating ability series was established: L-1 similar to L-2 similar to P"Bu-3 > PPh3 > P(O-2,4-Bu-t(2)-Ph)(3) > CO; indicating the carbenes investigated in this study to have a similar electronic cis-influence as trialkyl phosphines. Both complexes do not display hydroformylation activity towards 1-hexene in the absence of added phosphine or phosphite ligands under the conditions investigated (P = 60; T = 85 degrees C). In the presence of a phosphine or phosphite ligand the resulting hydroformylation catalysis was identical to that observed for [Rh(acac)(CO)(2)] and the corresponding ligand and subsequent high-pressure P-31 NMR studies confirmed substitution of the carbene ligand under these conditions. (c) 2005 Elsevier B.V. All rights reserved.