[(1,3-[N,N'-bis(1,5,9-triazacyclododecane)]propane)Zn2(methoxide)](3+) | 1072935-00-2

• 英文名称: [(1,3-[N,N'-bis(1,5,9-triazacyclododecane)]propane)Zn2(methoxide)](3+)
• 英文别名: Zn2(μ-methoxide)(1,3-bis-N1-(1,5,9-triazacyclododecyl)propane)；Zn2(methylate)(bis-N1,N1'-(1,5,9-triazacyclododecyl)propane)(3+)
• CAS: 1072935-00-2
• 化学式: C₂₂H₄₉N₆OZn₂
• 分子量: 544.451
• InChiKey: LAQSLTGMESNESJ-UHFFFAOYSA-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：
  None
• sp3杂化的碳原子比例：
  None
• 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：

  sodium methylate 、 1,3-(N,N'-bis(1,5,9-triazacycododecane))propane 、 zinc trifluoromethanesulfonate 以 甲醇 为溶剂， 生成 [(1,3-[N,N'-bis(1,5,9-triazacyclododecane)]propane)Zn2(methoxide)](3+)
  参考文献：
  名称：

  一系列 2-羟丙基芳基磷酸酯 RNA 模型的双核 Zn(II) 复合物催化环化：从限速 P-O 键裂解到底物结合机制的逐步变化

  摘要：

  制备了 1,3-[N,N'-双(1,5,9-三氮杂环十二烷)]丙烷 (1-Zn(II)2:(-OCH3)) 的甲醇桥连双核 Zn(II) 络合物，并通过停流分光光度法在甲醇中在 pH 9.8、T = 25°C 下研究了其对一系列 2-羟丙基磷酸芳基酯 (4a-g) 环化的催化作用。1-Zn(II)2:(-OCH3) 的氢氧化物类似物的 X 射线衍射结构，即 1-Zn(II)2:(-OH)，表明每个 Zn(II) 离子都是配位的由三氮杂环十二烷单元的三个 N 和一个桥连氢氧化物组成。底物 4a-g 的环化揭示了从 Michaelis-Menten 饱和动力学观察到的较差底物（4-OCH3 (4g); 4-H (4f); 3-OCH3 (4e); 4-Cl (4d); 3-NO2, (4c)) 到二级动力学（在 1-Zn(II)2:(-OCH3) 中线性）对于更好的底物（4-NO2，3-CH3

  DOI：

  10.1021/ja076847d

文献信息

• A Simple DNase Model System Comprising a Dinuclear Zn(II) Complex in Methanol Accelerates the Cleavage of a Series of Methyl Aryl Phosphate Diesters by 10¹¹−10¹³
  作者：Alexei A. Neverov、C. Tony Liu、Shannon E. Bunn、David Edwards、Christopher J. White、Stephanie A. Melnychuk、R. Stan Brown

  DOI：10.1021/ja8006963

  日期：2008.5.1

  The di-Zn(II) complex of 1,3-bis[N-1,N-1'-(1,5,9-triazacyclododecyl)] propane with an associated methoxide (3:Zn(II)(2):-OCH3) was prepared and its catalysis of the methanolysis of a series of fourteen methyl aryl phosphate diesters (6) was studied at (s)(s)pH 9.8 in methanol at 25.0 +/- 0.1 degrees C. Plots of k(obs) VS [3:Zn(II)(2):-OCH3](free) for all members of 6 show saturation behavior from which K-M and k(cat)(max) were determined. The second order rate constants for the catalyzed reactions (k(cat)(max)/K-M) for each substrate are larger than the corresponding methoxide catalyzed reaction (k(2)(-OMe)) by 1.4 x 10(8) to 3 x 10(9)-fold. The values of kcatmax for all members of 6 are between 4 x 10(11) and 3 x 10(13) times larger than the solution reaction at (s)(s)pH 9.8, with the largest accelerations being given for substrates where the departing aryloxy unit contains ortho-NO2 or C(= O)OCH3 groups. Based on the linear Bronsted plots of k(cat)(max) VS (s)(s)pK(a)of the phenol, beta(Ig) values of -0.57 and -0.34 are determined respectively for the catalyzed methanolysis of "regular' substrates that do not contain the ortho-NO2 or C(= O)OCH3 groups, and those substrates that do. The data are consistent with a two step mechanism for the catalyzed reaction with rate limiting formation of a catalyst-coordinated phosphorane intermediate, followed by fast loss of the aryloxy leaving group. A detailed energetics calculation indicates that the catalyst binds the transition state comprising [CH3O-:6]double dagger, giving a hypothetical [3:Zn(II)(2):CH3O-:6]double dagger complex, by -21.4 to -24.5 kcal/mol, with the strongest binding being for those substrates having the ortho-NO2 or C(= O)OCH3 groups.