[(2,6-(CH3)2C6H3N)2C12H6)Pd(CH2CH3)2] | 371160-69-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 吖萘类
• 英文名称: [(2,6-(CH3)2C6H3N)2C12H6)Pd(CH2CH3)2]
• CAS: 371160-69-9
• 化学式: C₃₂H₃₄N₂Pd
• 分子量: 553.055
• InChiKey: LZBQZVJPGOUNCU-CRLMKPFESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  tetrakis[3,5-bis(trifluoromethyl)phenyl]boric acid bis(diethyl ether) complex 、 [(2,6-(CH3)2C6H3N)2C12H6)Pd(CH2CH3)2] 以 二氯甲烷-D2 为溶剂， 生成 [(2,6-(CH3)2C6H3N)2C12H6)Pd(CH2CH3)(O(C2H5)2][B(3,5-(CF3)2C6H3)4]
  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
• 作为产物：
  描述：

  PdCl2(bis(o,o'-Me2C6H3-imino)acenaphthene) 、 乙基氯化镁 以 乙醚 为溶剂， 以26%的产率得到[(2,6-(CH3)2C6H3N)2C12H6)Pd(CH2CH3)2]
  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

文献信息

• Palladium(II) β-Agostic Alkyl Cations and Alkyl Ethylene Complexes:  Investigation of Polymer Chain Isomerization Mechanisms
  作者：Leigh H. Shultz、Daniel J. Tempel、Maurice Brookhart

  DOI：10.1021/ja011055j

  日期：2001.11.1

  NCMe, CO, and C2H4. Trapping with ethylene results in formation of cationic alkyl ethylene complexes which model the catalyst resting state in these systems. These complexes have been used to obtain mechanistic details and kinetic parameters of several processes, including isomerization of the alkyl ethylene complexes, associative and dissociative exchange with free ethylene, and migratory insertion

  通过相应的 (α-二亚胺)PdR2 (α-二亚胺 = 芳基取代二亚胺, R = n-Pr, n-Bu, i-Bu) 的一系列稳定的 Pd 二烷基配合物 ( α-二亚胺)PdCl2 络合物。这些二烷基物质在低温下的质子化导致烷烃的损失和阳离子 Pd β-正链烷基配合物的形成，这些配合物已被观察为这些 Pd 催化剂在乙烯和丙烯聚合中的中间体。介绍了这些烷基配合物的结构和动态行为的研究，以及这些物种与配体（如 NCMe、CO 和 C2H4）的捕获反应的结果。用乙烯捕获导致形成阳离子烷基乙烯配合物，其模拟了这些系统中的催化剂静止状态。这些配合物已被用于获得多个过程的机械细节和动力学参数，包括烷基乙烯配合物的异构化、与游离乙烯的缔合和解离交换以及伯和仲烷基乙烯物种的迁移插入率。这些研究表明，在由这些 Pd 催化剂生产的聚乙烯中观察到的总体支化受迁移插入动力学和涉及烷基乙烯配合物的平衡控制。