dirhodium(II) tetrakis(perfluorobutyrate)

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 卤代烷
• 英文名称: dirhodium(II) tetrakis(perfluorobutyrate)
• 英文别名: rhodium(II) perfluorobutyrate；Rh2(pfb)4；Rh2(perfluorobutyrate)4；rhodium(II) heptafluorobutyrate dimer；Rh2(CF3CF2CF2CO2)4；dirhodium(II)perfluorobutyrate；Rhodium(II) heptafluorobutryate dimer；2,2,3,3,4,4,4-heptafluorobutanoate;rhodium(2+)
• 化学式: C₁₆F₂₈O₈Rh₂
• 分子量: 1057.94
• InChiKey: BNCXPORMMOBRMR-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  2.27
• 重原子数：
  54
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  161
• 氢给体数：
  0
• 氢受体数：
  36

反应信息

• 作为反应物：
  描述：

  dirhodium(II) tetrakis(perfluorobutyrate) 、 乙硫醚 在 一氧化碳 作用下， 以 二氯甲烷 为溶剂， 生成 (diethylsulfide)(carbonyl)tetrakis(perfluorobutyrato)dirhodium(II)
  参考文献：
  名称：

  Bilgrien, Carl; Drago, Russell S.; Vogel, Glenn C., Inorganic Chemistry, 1986, vol. 25, # 16, p. 2864 - 2866

  摘要：

  DOI：
• 作为产物：
  描述：

  dirhodium tetraacetate 在 heptafluorobutanoic acid 、 heptafluorobutanoic anhydrite 作用下， 以 further solvent(s) 为溶剂， 以78%的产率得到dirhodium(II) tetrakis(perfluorobutyrate)
  参考文献：
  名称：

  全氟丁酸二铑（II）在温和条件下炔烃的高度区域选择性和立体选择性甲硅烷基甲酰化

  摘要：

  Addition to alkynes by organosilanes and carbon monoxide to form beta-silylacrylaldehydes (silylformylation) occurs efficiently in the presence of dirhodium(II) perfluorobutrate, Rh2(pfb)4, with turnover numbers that exceed 300. Reactions take place at atmospheric pressure and 0-degrees-C by controlled addition of the alkyne to the combination of organosilane and Rh2(pfb)4 or at 10 atm of CO without this control. Terminal alkynes are directed to silylformylation products in moderate to high yield with complete regiocontrol for carbonylation at the substituted carbon and with exceptional stereocontrol for the Z isomer (>10:1). Preferential silylformylation occurs with triethylsilane in competition with hydrosilylation, and this preference is greatly enhanced with the more reactive dimethylphenylsilane. With internal alkynes hydrosilylation is often dominant. At 1 atm of CO 3-butyn-2-one undergoes trimerization to 1,3,5-triacetylbenzene, and both CO and organosilane in combination with Rh2(pfb)4 are required, but at 10 atm of CO silylformylation occurs to the near exclusion of this trimerization reaction. Similar processes occur with methyl propynoate, but they are complicated by competitive hydrosilylation of the silylformylation product. The active catalyst for silylformylation is generated from Rh2(pfb)4 by CO association followed by hydrosilylation that generates trialkylsilyl perfluorobutyrate.

  DOI：

  10.1021/om00016a012
• 作为试剂：
  描述：

  2-环己烯-1-酮 、 二甲基苯基硅烷 在 dirhodium(II) tetrakis(perfluorobutyrate) 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以94%的产率得到(cyclohex-1-en-2-yloxy)dimethylphenylsilan
  参考文献：
  名称：

  四（全氟丁酸）四（二）吡啶鎓（II）催化的α，β-不饱和羰基化合物的1,4-氢化硅烷化。

  摘要：

  探索了在（1,4-β-不饱和酮和醛的1,4-氢硅烷化反应中）dirhodium（II）催化剂的使用。四（全氟丁酸酯）二铑（II）Rh2（pfb）4被证明是该方法的选择催化剂，可提供高收率的相应甲硅烷基烯醇醚。

  DOI：

  10.1248/cpb.54.1622

文献信息

• Carbon Dioxide as a Solubility “Switch” for the Reversible Dissolution of Highly Fluorinated Complexes and Reagents in Organic Solvents:  Application to Crystallization
  作者：Philip G. Jessop、Marilyn M. Olmstead、Christopher D. Ablan、Megan Grabenauer、Daniel Sheppard、Charles A. Eckert、Charles L. Liotta

  DOI：10.1021/ic020057h

  日期：2002.7.1

  Highly fluorinated organic or organometallic solid compounds can be made to dissolve in liquid hydrocarbons by the application of 20-70 bar of CO(2) gas. Subsequently releasing the gas causes the compounds to precipitate or crystallize, giving quantitative recovery of the solid. The resulting crystals can be of sufficient quality for single-crystal X-ray crystallography; the structures of Rh(2)(O(

  通过应用20-70 bar的CO（2）气体，可以使高度氟化的有机或有机金属固体化合物溶解在液态烃中。随后释放气体使化合物沉淀或结晶，从而定量回收固体。所得晶体对于单晶X射线晶体学而言可能具有足够的质量；Rh（2）（O（2）CCF（2）CF（2）CF（3））（4）（DMF）（2），Rh（2）（O（2）C（CF（2））的结构）（9F）（4）（MeOH）（2），Cr（hfacac）（3）和P [C（6）H（3）（3,5-CF（3））（2）]] [ 3）已经从以这种方式生长的晶体中确定。
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: Rh: SVol.B2, 1.1.2.4, page 47 - 48
  作者：

  DOI：——

  日期：——
• Magnetic exchange interactions in nitroxyl biradicals bridged by metal-metal bonded complexes: structural, magnetochemical, and electronic spectral characterization of tetrakis(perfluorocarboxylato)dimetal(II) complexes of rhodium and molybdenum containing axially coordinated nitroxyl radicals
  作者：Timothy R. Felthouse、Teng Yuan. Dong、David N. Hendrickson、Huey Sheng. Shieh、Michael R. Thompson

  DOI：10.1021/ja00286a016

  日期：1986.12
• Schurig, Volker, Inorganic Chemistry, 1986, vol. 25, # 7, p. 945 - 949
  作者：Schurig, Volker

  DOI：——

  日期：——
• Comparison of the coordination chemistry and inductive transfer through the metal-metal bond in adducts of dirhodium and dimolybdenum carboxylates
  作者：Russell S. Drago、John R. Long、Richard Cosmano

  DOI：10.1021/ic00136a013

  日期：1982.6