1,3-bis(trifluoromethyl)benzene-5-ide;bromorhodium(2+);1,2,3,4,5-pentamethylcyclopenta-1,3-diene;trimethylphosphane | 172220-20-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1,3-bis(trifluoromethyl)benzene-5-ide;bromorhodium(2+);1,2,3,4,5-pentamethylcyclopenta-1,3-diene;trimethylphosphane
• CAS: 172220-20-1
• 化学式: C₂₁H₂₇BrF₆PRh
• 分子量: 607.219
• InChiKey: OWGMYUAUSHRDNZ-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  8.67
• 重原子数：
  30
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为产物：
  描述：

  三溴甲烷 、 1,3-bis(trifluoromethyl)benzene-5-ide;1,2,3,4,5-pentamethylcyclopenta-1,3-diene;rhodium(2+) monohydride;trimethylphosphane 以 苯 为溶剂， 生成 1,3-bis(trifluoromethyl)benzene-5-ide;bromorhodium(2+);1,2,3,4,5-pentamethylcyclopenta-1,3-diene;trimethylphosphane
  参考文献：
  名称：

  取代基对二取代芳基氢化物络合物的还原反应的影响：机理和热力学方面的考虑

  摘要：

  The complexes (C(5)Me(5))Rh(PMe(3))(3,5-C(6)H(3)R(2))H for R = C(CH3)(3), CH(CH3)(2), Si(CH3)(3), CH3, and CF3 (1c-g) have been prepared both by irradiation of (C(5)Me(5))Rh(PMe(3))(C2H4) in neat arene and by thermolysis of (C(5)Me(5))Rh(PMe(3))(Ph)H (1a) in neat arene, Quenching the hydride species with CHBr3 allowed isolation of the corresponding bromide complexes (C(5)Me(5))Rh(PMe(3))(3,5-C(6)H(3)R(2))Br (2c-g). Rates of reductive elimination of arene for the series of disubstituted aryl hydride complexes were measured at various temperatures and activation parameters Delta H-double dagger and Delta S-double dagger obtained and compared with those of (C(5)Me(5))-Rh(PMe(3))(Ph)H (1a) and (C(5)Me(5))Rh(PMe(3))(tolyl)H (1b). Delta H-double dagger values range from +35 to +18 kcal/mol, and Delta S-double dagger values range from +16.4 to -19 cal/mol K. Laser flash photolysis experiments using (C(5)Me(5))Rh(PMe(3))(C2H4) in neat toluene at various temperatures allowed the determination of activation parameters Delta H-double dagger and Delta S-double dagger for intramolecular C-H bond oxidative addition of the eta(2)-arene complex 3b. Equilibrium measurements allowed determination of Delta G degrees values for several of the disubstituted aryl hydride complexes versus the parent phenyl hydride complex. A kinetic isotope effect of h(H)/h(D) = 1.0 +/- 0.1 was measured for the reaction of (C(5)Me(5))Rh(PMe(3))(C2H4) with a 1:1 mixture of 5-deuterio-1,3-di-tert-butylbenzene and 1,3-di-tert-butylbenzene. The equilibrium isotope effect for the same reaction K-eq = 2.27(1) favors the aryl hydride and free deuterated arene.

  DOI：

  10.1021/om00012a038