trans-[Co(dimethylglyoximate)2(CH2Ph)(MeOH)] | 735272-31-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: trans-[Co(dimethylglyoximate)2(CH2Ph)(MeOH)]
• 英文别名: trans-[(CF3CH2)Co(Hdmg)2(CH3OH)]；trans-[(C6H5CH2)Co(dimethylglyoximate)2(methanol)]
• CAS: 735272-31-8
• 化学式: C₁₆H₂₅CoN₄O₅
• 分子量: 412.392
• InChiKey: PFHODLDSKBVOEE-DVTASQICSA-L

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

• 作为反应物：
  描述：

  trans-[Co(dimethylglyoximate)2(CH2Ph)(MeOH)] 、 三苯基膦 以 甲醇 为溶剂， 生成 trans-[Co(dimethylglyoximate)2(CH2Ph)(triphenylphoshine)]
  参考文献：
  名称：

  Mechanistic Elucidation of the Substitution Behavior of Alkyl Cobaloximes in Water and Methanol as Solvents

  摘要：

  The ligand substitution behavior of trans-[Co(HdMg)(2)(R)S] (R = CH3, PhCH2; Hdmg = dimethylglyoximate; S = H2O and/or MeOH) was studied for imidazole, pyrazole, 1,2,4-triazole, N-acetylimidazole, 5-chloro-1-methylimidazole, NO2-, Ph3P, Ph3As, and Ph3Sb as entering ligands. In all cases, except for Ph3As and Ph3Sb, the observed kinetics shows a linear dependence on the entering nucleophile concentration with no evidence for a back reaction. In the case of Ph3As and Ph3Sb as entering nucleophiles, kinetic evidence for a reverse solvolysis reaction is at hand. Activation parameters (DeltaH(+), DeltaS(+), and DeltaV(+)) were determined from the temperature and pressure dependence of all studied reactions and support the operation of a dissociatively activated substitution mechanism. The rate and activation parameters show that there is an increase in the dissociative character from a dissociative interchange to a limiting dissociative mechanism that depends on the nature of R and the entering nucleophile. The crystal structure of trans-[Co(en)(2)(Me)H2O](2+) was determined by X-ray analysis. The Co-O and Co-C bond lengths were found to be 2.153(6) and 1.995(10) Angstrom, respectively. The kinetic and structural data are discussed in reference to a series of earlier studied systems for which data are reported in the literature.

  DOI：

  10.1021/ic049761j

文献信息

• Kinetics and Mechanism of Axial Ligand Substitution of Alkyl Cobaloximes by Substituted Pyridines in Different Solvents
  作者：Basam M. Alzoubi、Mohamed S. A. Hamza、Alessandro Felluga、Lucio Randaccio、Giovanni Tauzher、Rudi van Eldik

  DOI：10.1002/ejic.200300733

  日期：2004.2

  (4-NH2Py), pyridine (Py) and 4-cyanopyridine (4-CNPy). From the pressure and temperature dependence of the substitution of methanol by 4-NH2Py, Py, and 4-CNPy, the activation parameters ΔH≠, ΔS≠, and ΔV≠ were estimated for the cases where R = PhCH2 and CF3CH2. The activation parameters for the substitution of H2O by Py and 4-CNPy in the case where R = CF3CH2 were also found. The kinetic data and activation

  针对亲核试剂 4-氨基吡啶 (4-NH2Py)、吡啶 (Py) 和反式 RCo(Hdmg)2S（其中 R = PhCH2 或 CF3CH2，Hdmg = 二甲基乙醛肟，S = H2O 或 MeOH）的配体取代反应进行了研究4-氰基吡啶 (4-CNPy)。根据 4-NH2Py、Py 和 4-CNPy 替代甲醇的压力和温度依赖性，估计活化参数 ΔH≠、ΔS≠ 和 ΔV≠ 的情况，其中 R = PhCH2 和 CF3CH2。在 R = CF3CH2 的情况下，还发现了 Py 和 4-CNPy 取代 的激活参数。动力学数据和活化参数表明，随着 R 基团从 PhCH2 变为 CF3CH2 以及溶剂从 MeOH 变为 ，反应的解离特性降低。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)