[Pd(η(1),η(2)-C8H12OMe)bipy](+)CF3SO3(-) | 154096-20-5

• 英文名称: [Pd(η(1),η(2)-C8H12OMe)bipy](+)CF3SO3(-)
• CAS: 154096-20-5
• 化学式: CF₃O₃S*C₁₉H₂₃N₂OPd
• 分子量: 550.895
• InChiKey: DHHYKDMRRQGCMF-ADOAOARYSA-M

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：

  2,2'-联吡啶 、 {Pd(μ-chloro)(σ,π-8-methoxy-cycloocten-1-yl)}2 、 三氟甲磺酸钠 以 甲醇 为溶剂， 以40%的产率得到[Pd(η(1),η(2)-C8H12OMe)bipy](+)CF3SO3(-)
  参考文献：
  名称：

  Counterion Effect on CO/Styrene Copolymerization Catalyzed by Cationic Palladium(II) Organometallic Complexes:  An Interionic Structural and Dynamic Investigation Based on NMR Spectroscopy

  摘要：

  Complexes [Pd(eta(1),eta(2)-C8H12OMe)bipy]X-+(-) (2a-f) (where X = BPh4- (a), CF3SO3- (b), BF4- (C), PF6- (d), SbF6- (e), and B(3,5-(CF3)(2)C6H3)(4)(-) (f); bipy = 2,2'-bipyridine; C8H12OMe = cyclooctenylmethoxy group) were synthesized by the reaction of the dimer [Pd(eta(1),eta(2)-C8H12OMe)Cl](2) (1) with the bipy ligand in methanol containing Y+X- salts. They were characterized in solution by multinuclear and multidimensional NMR spectroscopy. The solid-state structure of complex 2d was obtained by X-ray single-crystal investigation. The catalytic activity of complexes 2 toward CO/styrene copolymerization in methylene chloride was tested and related to the type of counterion. The order of the catalytic activity of complexes 2a-f is the following: BPh4- << CF3SO3- < BF4- < PF6- < SbF6- < B(3,5-(CF3)(2)C6H3)(4)(-) If the copolymerization reactions are carried out in the presence of an excess of the bipy ligand, the anion effect is less important and the order is the following: BPh4- << CF3SO3- < BF4- approximate to B(3,5-(CF3)(2)C6H3)(4-) approximate to PF6- approximate to SbF6-. The interionic structure of all complexes was investigated in CD2Cl2 at room and low temperature by F-19{H-1} HOESY and H-1 NOESY NMR spectroscopies. In solution, the counterions are located above or below the bipy ligand shifted toward the pyridine ring trans to the Pd-C sigma bond, while in the crystal structure of 2d, they are settled sideways to the cationic moiety. The best anion in catalysis is the least strong coordinating one that shows the weakest interionic contacts in the F-19(H-1) HOESY or 1H NOESY NMR spectra. The dynamic process that exchanges the two pyridyl rings was investigated by variable-temperature NMR spectroscopy in CD2Cl2. The activation parameters were determined. Delta G(298)(double dagger) values range from 54 to 58kJ/mol. The negative values of Delta S-double dagger (-58/-108 J K-1 mol(-1)), for all compounds, with the exception of 2f, suggest an associative mechanism.

  DOI：

  10.1021/om990372k