(Cr*2Zr(N(CH3)2C6H5)CH2CH(CH3)CH2CH=CH2)(B(C6F5)4) | 295359-20-5

• 英文名称: (Cr*2Zr(N(CH3)2C6H5)CH2CH(CH3)CH2CH=CH2)(B(C6F5)4)
• CAS: 295359-20-5
• 化学式: C₂₄BF₂₀*C₃₄H₅₂NZr
• 分子量: 1245.06
• InChiKey: BJOUWMZRPAUQLI-UHFFFAOYSA-N

反应信息

• 作为产物：
  描述：

  [(η5-C5Me5)2Zr(μ-CH2)2C(H)(CH2CHCH2)] 、 N,N-二甲基苯铵四(五氟苯基)硼酸盐 以 二氯甲烷-D2 为溶剂， 生成 (Cr*2Zr(N(CH3)2C6H5)CH2CH(CH3)CH2CH=CH2)(B(C6F5)4)
  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