[(η(5)-C5H3Me2)2ZrMe][MeB(perfluorophenyl)3] | 133445-51-9

• 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: [(η(5)-C5H3Me2)2ZrMe][MeB(perfluorophenyl)3]
• 英文别名: carbanide;1,5-dimethylcyclopenta-1,3-diene;methyl-tris(2,3,4,5,6-pentafluorophenyl)boranuide;zirconium(4+)
• CAS: 133445-51-9
• 化学式: C₁₅H₂₁Zr*C₁₉H₃BF₁₅
• 分子量: 819.576
• InChiKey: MFCGPCYEOCWVIA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.37
• 重原子数：
  51
• 可旋转键数：
  3
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.15
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  19

反应信息

• 作为产物：
  描述：

  bis(1,2-dimethylcyclopentadienyl)zirconocene(Me)(CH2CMe3) 、 三(五氟苯基)硼烷 以 氘代甲苯 为溶剂， 生成 [(η(5)-C5H3Me2)2ZrMe][MeB(perfluorophenyl)3]
  参考文献：
  名称：

  Metal-Alkyl Group Effects on the Thermodynamic Stability and Stereochemical Mobility of B(C₆F₅)₃-Derived Zr and Hf Metallocenium Ion-Pairs

  摘要：

  This paper reports significant dependence of ion-pair formation energetics and stereomutation rates upon the metal-bound alkyl substituent (R) and the solvent dielectric constant in the metallocenium series (1,2-Me2Cp)(2)MR+ MeB(C6F5)(3)(-) where R = Me, (CH2Bu)-Bu-t, CH2TMS, CH(TMS)(2), and M = Zr and Hf, as determined by reaction titration calorimetry and dynamic NMR spectroscopy. For the ion-pair forming reaction, (1,2 Me2Cp)(2)M(R)Me + B(C6F5)(3) --> (1,2-Me2Cp)(2)MR+ MeB(C6F5)(3)(-), enthalpies in toluene solution at 25 degreesC for M = Zr and R = Me, CH2TMS, and CH(TMS)(2) are -24.6(0.8), -22.6(1.0), and -59.2(1.4) kcal/mol, respectively. Corresponding values for M = Hf and R = Me and CH2TMS are -20.8(0.5) and -31.1(1.6) kcal/mol, respectively. DeltaH double dagger (reorg) values for the reorganization process that interchanges the ion-pair enantiotopic sites for M = Zr and R = Me, (CH2Bu)-Bu-t, CH2TMS, and CH(TMS)(2) are 22(1), 18(1), 17(1), and 9(2) kcal/mol, respectively. Corresponding DeltaH double dagger (reorg) values for M = Hf and R = Me, (CH2Bu)-Bu-t, and CH2TMS are >24, 12(3), and 15(2) kcal/mol, respectively. DeltaH double dagger (reorg) values are highest in low dielectric constant solvents such as C6D12 Activation parameters for beta -Me elimination in the complexes (1,2-Me2Cp)(2)(MCH2Bu+)-Bu-t MeB(C6F5)(3)(-) for M = Zr and Hf are found to be DeltaH double dagger (beta -Me) = 22.5(0.9) and 17.3(0.9) kcal/mol, and DeltaS double dagger (beta -Me) = 4.3(3.3) and -11.9(3.4) cal/mol(.)K, respectively.

  DOI：

  10.1021/ja000810a