bis(1,2-dimethylcyclopentadienyl)[bis(trimethylsilyl)methyl]-zirconium(IV) methyl-trispentafluorophenylborate | 230975-25-4

• 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: bis(1,2-dimethylcyclopentadienyl)[bis(trimethylsilyl)methyl]-zirconium(IV) methyl-trispentafluorophenylborate
• 英文别名: 1,5-dimethylcyclopenta-1,3-diene;methyl-tris(2,3,4,5,6-pentafluorophenyl)boranuide;trimethyl(trimethylsilylmethyl)silane;zirconium(4+)
• CAS: 230975-25-4
• 化学式: C₁₉H₃BF₁₅*C₂₁H₃₇Si₂Zr
• 分子量: 963.94
• InChiKey: KYKSSJJNYSODTG-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

• 作为产物：
  描述：

  methylbis(1,2-dimethylcyclopentadienyl)[bis(trimethylsilyl)methyl]zirconium(IV) 、 三(五氟苯基)硼烷 以 甲苯 为溶剂， 以92%的产率得到bis(1,2-dimethylcyclopentadienyl)[bis(trimethylsilyl)methyl]-zirconium(IV) methyl-trispentafluorophenylborate
  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

文献信息

• Metal-Alkyl Group Effects on the Thermodynamic Stability and Stereochemical Mobility of B(C₆F₅)₃-Derived Zr and Hf Metallocenium Ion-Pairs
  作者：Colin L. Beswick、Tobin J. Marks

  DOI：10.1021/ja000810a

  日期：2000.10.1

  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.