Rh(I)(O3S(C6H4)CH2C(CH2P(C6H5)2)3)(cycloocta-1,5-diene) | 172221-17-9

• 英文名称: Rh(I)(O3S(C6H4)CH2C(CH2P(C6H5)2)3)(cycloocta-1,5-diene)
• 英文别名: (O3SC6H4CH2C(CH2PPh2)3)Rh(1,5-cyclooctadiene)
• CAS: 172221-17-9
• 化学式: C₅₅H₅₄O₃P₃RhS
• 分子量: 990.925
• InChiKey: ZPLOVAOKSNIKPP-GHDUESPLSA-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：

  Rh(I)(O3S(C6H4)CH2C(CH2P(C6H5)2)3)(cycloocta-1,5-diene) 、 potassium tert-butylate 、 苯并噻吩 在 氢气 作用下， 以 甲醇 为溶剂， 以90%的产率得到
  参考文献：
  名称：

  Liquid-Biphase Hydrogenolysis of Benzo[b]thiophene by Rhodium Catalysis

  摘要：

  The catalytic activity of the zwitterionic complex [(sulphos)Rh(cod)] for the hydrogenation and hydrogenolysis reactions of benzo[b]thiophene (BT) has been studied in either methanol or liquid-biphase systems comprising MeOH or MeOH-H2O as the polar phase and n-heptane as the organic phase [sulphos = -O3S(C6H4)CH2C(CH2PPh2)(3)]. The catalyst activity is independent of the phase variation. Under neutral conditions, the slow but selective hydrogenation of BT to 2,3-dihydrobenzo[b]thiophene is observed. Conversely, in the presence of NaOH or other strong bases, the fast and selective hydrogenolysis of BT to 2-ethylthiophenol sodium salt occurs. In a typical liquid-biphase hydrogenolysis reaction [35 mg (0.035 mmol) of catalyst, 470 mg (3.5 mmol) of BT, 180 mg (4.5 mmol) of NaOH, 5 mt of MeOH, 5 mL of H2O, 10 mL of n-heptane, 30 bar of H-2, 160 degrees C], all the substrate is practically consumed in ca. 5 h to give the 2-ethylthiophenolate product. The strong base plays a dual role in the hydrogenolysis reaction: it promotes the formation of the Rh-H species (which is necessary for the C-S insertion step) by heterolytic splitting of H-2 and accelerates the conversion of BT by aiding the reductive elimination of the hydrogenolysis product. The effect of the H-2 pressure and of the substrate, catalyst, and base concentrations on the conversion rate of BT has been studied under liquid-biphase conditions. High-pressure NMR experiments in sapphire tubes have provided mechanistic information on the catalysis cycle for the hydrogenolysis of BT in MeOH. Under catalytic conditions, the phosphorus-containing rhodium compounds (visible on the NMR time scale) are the trihydride [(sulphos)RhH3](-) and the dihydride 2-ethylthiophenolate complex [(sulphos)Rh(H)(2)(o-S(C6H4)C2H5)](-). Consistent with previous studies, the reductive elimination of the thiol from the metal center is suggested to be the rate-determining step of the hydrogenolysis reaction of BT catalyzed by the 16e(-) fragment [(sulphos)RhH](-).

  DOI：

  10.1021/ja9641517
• 作为产物：
  描述：

  di-μ-chloro-bis(1,5-cyclooctadiene)dirhodium 、 Na(O3SC6H4CH2C(CH2PPh2)3) 生成 Rh(I)(O3S(C6H4)CH2C(CH2P(C6H5)2)3)(cycloocta-1,5-diene)
  参考文献：
  名称：

  Zwitterionic Metal Complexes of the New Triphosphine NaO3S(C6H4)CH2C(CH2PPh2)3 in Liquid Biphasic Catalysis: An Alternative to Teflon "Ponytails" for Facile Catalyst Separation without Water

  摘要：

  The new Ligand NaO3S(C6H4)CH2C(CH(2)PPh(2))(3) (sulphos) has been synthesized. The application of the zwitterionic Rh(I) complexes (sulphos)Rh(cod) and (sulphos)Rh(CO)(2) in liquid biphasic catalysts has been demonstrated for the hydrogenation of styrene and the hydroformylation of 1-hexene, respectively. The Latter reaction gives C-7 alcohols in an alcohol/hydrocarbon system and C-7 aldehydes in an alcohol-water/hydrocarbon system. All rhodium a's recovered in the polar phase at the end of the catalytic reactions.

  DOI：

  10.1021/om00012a002