Cr*2Zr(THF)CH2CH(CH2B(C6F5)3)CH2CH=CH2 | 250143-79-4

• 英文名称: Cr*2Zr(THF)CH2CH(CH2B(C6F5)3)CH2CH=CH2
• CAS: 250143-79-4
• 化学式: C₄₈H₄₈BF₁₅OZr
• 分子量: 1027.92
• InChiKey: NZNVSDVIQNECMG-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：

  四氢呋喃 、 Cr*2Zr(η1,η2-CH2CH(CH2B(C6F5)3)CH2CH=CH2) 以 二氯甲烷-D2 为溶剂， 生成 Cr*2Zr(THF)CH2CH(CH2B(C6F5)3)CH2CH=CH2
  参考文献：
  名称：

  Measurement of Barriers for Alkene Dissociation and for Inversion at Zirconium in a d⁰ Zirconium−Alkyl−Alkene Complex

  摘要：

  The beta-allyl zirconacyclobutane complex Cp*Zr-2[CH2CH(CH2CH=CH2)CH2] (7) reacted rapidly with B(C6F5)(3) in CD2Cl2 at -78 degrees C to form the zwitterionic d(0) zirconium(IV) chelate complex Cp*Zr-2[eta(1),eta(2)-CH2CH[CH2B(C6F5)(3)]CH2CH=CH2] (2a and 2b). Low-temperature H-1, C-13, TOCSY1D, and NOESY1D NMR spectroscopy of 2 established the bending of the tethered alkene to the d(0) metal center. A dynamic NMR study of the interconversion of 2a and 2b allowed measurement of the alkene dissociation energy (Delta G(double dagger) = 10.5 (2a to 2b) and 10.3 (2b to 2a) kcal mol(-1)), but the complex decomposed before the barrier for site epimerization at the zirconium center could be determined. Reaction of 7 with [(C6H5)(2)(CH3)NH][B(C6F5)(4)] led to the formation of two isomeric d(0) zirconium(IV)-alkyl-alkene chelates Cp*Zr-2[eta(1),eta(2)-CH2CH(CH3)CH2CH=CH2] [B(C6F5)(4)] (8a and 8b). This more thermally stable zirconium alkyl-alkene complex allowed the measurement of barriers associated with decomplexation of the alkene (Delta G(double dagger) = 10.7 and 11.1 kcal mol(-1)) and site epimerization at the zirconium center (Delta G(double dagger) =14.4 kcal mol(-1)) by line shape analysis of variable-temperature H-1 and C-13 NMR spectra.

  DOI：

  10.1021/om9908940

文献信息

• Observation of Zwitterionic d⁰ Zirconium−Alkyl−Alkene Chelates:  Models for Intermediates in Metallocene-Catalyzed Alkene Polymerizations
  作者：Charles P. Casey、Donald W. Carpenetti、Hidehiro Sakurai

  DOI：10.1021/ja9919837

  日期：1999.10.1