Rh2(μ-S(CH2)3Si(OCH3)3)2(CO)4 | 210221-89-9

• 英文名称: Rh2(μ-S(CH2)3Si(OCH3)3)2(CO)4
• 英文别名: [Rh(μ-S(CH2)3Si(OCH3)3)(CO)2]2；[Rh(μ-S(CH2)3Si(OCH3)3)CO)2]2
• CAS: 210221-89-9
• 化学式: C₁₆H₃₀O₁₀Rh₂S₂Si₂
• 分子量: 708.522
• InChiKey: AKSYVLKRDMGMPG-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  Rh2(μ-S(CH2)3Si(OCH3)3)2(CO)4 、 二苯基[3-(三乙氧基甲硅烷基)丙基]膦 以 甲苯 为溶剂， 生成 cis-Rh2[μ-S(CH2)3Si(OCH3)3]2[Ph2P(CH2)3Si(OC2H5)3]2(CO)2
  参考文献：
  名称：

  Hydroformylation of 1-Octene under Atmospheric Pressure Catalyzed by Rhodium Carbonyl Thiolate Complexes Tethered to Silica

  摘要：

  The silica-tethered rhodium thiolate complex catalysts Rh-S/SiO2 and Rh-S-P/SiO2 were prepared by the condensation of SiO2 with Rh-2[mu-S(CH2)(3)Si(OCH3)(3)](2)(CO)(4) (Rh-S) or Rh-2[mu-S(CH2)(3)Si(OCH3)(3)](2)[Ph2P(CH2)(3)Si(OC2H5)(3)](2)(CO)(2) (Rh-S-P). These tethered complex catalysts exhibit high activity for the hydroformylation of 1-octene in the presence of phosphine donor ligands under the mild conditions of 60 degrees C and 1 atm. IR (DRIFT) spectral studies of the catalysts used indicate that tethered monorhodium dicarbonyl thiolate complexes of the type Rh(SR)(CO)(2)(PR'(3)) are the predominant species on the surface for the catalysts that have the highest hydroformylation activity. The catalysts are easily separated from the reaction mixtures, and the Rh-S/SiO2 Catalyst maintains its activity through at least three cycles over a total period of 69 h, during which time there are 1273 (mol of aldehyde/mol of Rh) turnovers. Effects of the phosphine ligand and PR'(3)/Rh mole ratio on the hydroformylation rate, conversion, and chemo- and regioselectivity for aldehyde products were also investigated.

  DOI：

  10.1021/om9800795
• 作为产物：
  描述：

  巯丙基三甲氧基硅烷 、 di(rhodium)tetracarbonyl dichloride 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 生成 Rh2(μ-S(CH2)3Si(OCH3)3)2(CO)4
  参考文献：
  名称：

  Hydroformylation of 1-Octene under Atmospheric Pressure Catalyzed by Rhodium Carbonyl Thiolate Complexes Tethered to Silica

  摘要：

  The silica-tethered rhodium thiolate complex catalysts Rh-S/SiO2 and Rh-S-P/SiO2 were prepared by the condensation of SiO2 with Rh-2[mu-S(CH2)(3)Si(OCH3)(3)](2)(CO)(4) (Rh-S) or Rh-2[mu-S(CH2)(3)Si(OCH3)(3)](2)[Ph2P(CH2)(3)Si(OC2H5)(3)](2)(CO)(2) (Rh-S-P). These tethered complex catalysts exhibit high activity for the hydroformylation of 1-octene in the presence of phosphine donor ligands under the mild conditions of 60 degrees C and 1 atm. IR (DRIFT) spectral studies of the catalysts used indicate that tethered monorhodium dicarbonyl thiolate complexes of the type Rh(SR)(CO)(2)(PR'(3)) are the predominant species on the surface for the catalysts that have the highest hydroformylation activity. The catalysts are easily separated from the reaction mixtures, and the Rh-S/SiO2 Catalyst maintains its activity through at least three cycles over a total period of 69 h, during which time there are 1273 (mol of aldehyde/mol of Rh) turnovers. Effects of the phosphine ligand and PR'(3)/Rh mole ratio on the hydroformylation rate, conversion, and chemo- and regioselectivity for aldehyde products were also investigated.

  DOI：

  10.1021/om9800795

文献信息

• Effects of supported donor ligands on the activity and stability of tethered rhodium complex catalysts for hydroformylation
  作者：L Huang

  DOI：10.1016/j.molcata.2003.10.007

  日期：2004.3.15

  Functionalized SiO2-tethered rhodium complexes derived from Rh4(CO)12, RhCl(PPh3)3 and RhHCl(PPh3)3 have been studied by infrared spectroscopy (IR) and solid state NMR. Rh4(CO)12 and phosphinated or aminated SiO2 are suggested to form Rh4(CO)12−xLx (L: supported PPh2 or NH2; x=2 or 3). Rh4(CO)12 reacts with thiolated SiO2 to give [Rh(μ-L)(CO)2]2 (L: supported SH). The reaction of RhCl(PPh3)3 or RhH(CO)(PPh3)3

  已通过红外光谱（IR）和固态NMR研究了衍生自Rh 4（CO）12，RhCl（PPh 3）3和RhHCl（PPh 3）3的功能化SiO 2系铑配合物。建议使用Rh 4（CO）12和磷化或胺化的SiO 2形成Rh 4（CO）12- x L x（L：负载的PPh 2或NH 2；x = 2或3）。Rh 4（CO）12与硫醇化的SiO 2反应给出[Rh（μ-L）（CO）2 ] 2（L：支持的SH）。假设RhCl（PPh 3）3或RhH（CO）（PPh 3）3与官能化SiO 2的反应产生RhCl（PPh 3）2 L或RhH（CO）（PPh 3）2 L（L：负载PPh 2或NH 2或SH）。
• Rh4(CO)12-derived functionalized MCM-41-tethered rhodium complexes: preparation, characterization and catalysis for cyclohexene hydroformylation
  作者：L. Huang、J.C. Wu、S. Kawi

  DOI：10.1016/s1381-1169(03)00423-0

  日期：2003.10

  The preparation of Rh-4(CO)(12)-derived functionalized silicate MCM-41-tethered catalysts has been studied by infrared (IR) spectroscopy, X-ray diffraction (XRD) and N-2 adsorption-desorption. Silicate MCM-41 is first functionalized with phosphine, amine and thiol donor ligand groups. Then the functionalized MCM-41 is reacted with Rh-4(CO)(12) by coordination of surface donor ligands to the rhodium to produce phosphinated and aminated MCM-41-tethered unidentified rhodium carbonyl clusters and MCM-41-tethered [Rh(mu-S(CH2)(3)Si(O-s)(3))(CO)(2)](2) (where O-s represents surface oxygen). The functionalized MCM-41 and Rh/functionalized MCM-41 possess the structural ordering of mesoporous MCM-41, but exhibit reduced pore sizes, total pore volumes and BET surface areas. The tethered rhodium carbonyl catalysts behave differently with different donor ligands attached in cyclohexene hydroformylation under equimolar CO and H-2 at 2.7 MPa and 100 degreesC. Only the aminated MCM-41-tethered catalyst displays good activity, selectivity and recycling for the formation of cyclohexane carboxaldehyde. The influences of supported donor ligands on the activity and stability of tethered catalysts for hydroformylation are discussed. The mesoporous structure of MCM-41 is maintained stable during the catalytic reaction. (C) 2003 Elsevier B.V. All rights reserved.