| 371160-80-4

• CAS: 371160-80-4
• 化学式: C₃₂H₁₂BF₂₄*C₃₈H₄₅N₂Pd
• 分子量: 1500.42
• InChiKey: DFKJWMCSYJBOSH-RQYPTFNSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  [(2,6-(CH(CH3)2)2C6H3N)2C12H6)Pd((13)CH2CH3)2] 、 以 further solvent(s) 为溶剂， 生成 、
  参考文献：
  名称：

  Measurement of the Barrier to β-Hydride Elimination in a β-Agostic Palladium−Ethyl Complex:  A Model for the Energetics of Chain-Walking in (α-Diimine)PdR⁺ Olefin Polymerization Catalysts

  摘要：

  The cationic Pd(II) ethyl complex [[(2,6-(Pr-i)(2)C6H3)N=C(An)C(An)=N(2,6-(Pr-i)(2)C6H3)]Pd(CH2-CH2-mu -H)]BAr'(4) (8), which exhibits beta -agostic interaction, has been synthesized via protonation of the corresponding diethyl complex with H(OiPr(2))(2)BAr'(4) (Ar' = 3,5-(CF3)(2)C6H3). The fluxional behavior of this ethyl cation has been studied quantitatively using H-1 and C-13 NMR spectroscopy. Two dynamic processes have been observed: (1) beta -H elimination and reinsertion with opposite regiochemistry and (2) rotation about the C-C bond of the ethyl group. beta -H elimination is the lower energy process, with DeltaG(double dagger) = 7.1 kcal/mol at -108 degreesC. Eyring analysis of the C-13 NMR data indicates DeltaH(double dagger) = 6.1 +/- 0.2 kcal/mol and DeltaS(double dagger) = -5.2 +/- 0.9 eu. Rotation of the agostic methyl group occurs with DeltaG(double dagger) ca. 8.4 kcal/mol at -108 degreesC. These data provide insight into the energetics of chain walking, which is responsible for the unusual polyolefin microstructures produced using (alpha -diimine)PdR+ catalysts.

  DOI：

  10.1021/om010197j