bis(1,2-dimethylcyclopentadienyl)zirconocene(Me)(CH2CMe3) | 230975-17-4

• 分子结构分类: 有机化合物 - 碳氢化合物 - 芳香烃
• 英文名称: bis(1,2-dimethylcyclopentadienyl)zirconocene(Me)(CH2CMe3)
• 英文别名: bis(1,2-dimethylcyclopentadienyl)methyl(neopentyl)zirconium(IV)；carbanide;1,5-dimethylcyclopenta-1,3-diene;2-methanidyl-2-methylpropane;zirconium(4+)
• CAS: 230975-17-4
• 化学式: C₂₀H₃₂Zr
• 分子量: 363.698
• InChiKey: LTRRCDDJLPJOOR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 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：

  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
• 作为产物：
  描述：

  bis(1,2-dimethylcyclopentadienyl)zirconocene(CH2CMe3)(CH3B(C6F5)3) 生成 bis(1,2-dimethylcyclopentadienyl)zirconocene(Me)(CH2CMe3)
  参考文献：
  名称：

  锆-烷基对锆烯醇烷基中离子对形成热力学和结构重组动力学的重要影响

  摘要：

  在[（1,2-Me 2 Cp）2 ZrR] + [CH 3 B（C 6）中报告了大量的Zr-烷基（R）对离子对热力学稳定性以及离子对溶液结构和结构动力学的影响F 5）3 ] -系列，其中R = CH 3，CH 2 C（CH 3）3，CH 2 Si（CH 3）3和CH [Si（CH 3）3 ] 2。这些定量结果强调了这样的R部分可能在第4族茂金属介导的烯烃聚合催化中发挥的作用。

  DOI：

  10.1021/om990274z