trimethylsilylium trifluoromethanesulfonate pyridine-d5 | 1361182-58-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: trimethylsilylium trifluoromethanesulfonate pyridine-d5
• 英文别名: trimethylsilylium trifluoromethanesulfonate pyridine-d₅
• CAS: 1361182-58-2
• 化学式: CF₃O₃S*C₈H₁₄NSi
• 分子量: 306.322
• InChiKey: BBSGVIARQUWZID-REAAFBMTSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  1.71
• 重原子数：
  18.0
• 可旋转键数：
  1.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  61.08
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为产物：
  描述：

  氘代吡啶 、 三氟甲磺酸三甲基硅酯 以 二氯甲烷 为溶剂， 生成 trimethylsilylium trifluoromethanesulfonate pyridine-d5
  参考文献：
  名称：

  甲硅烷基三氟甲磺酸酯的路易斯酸度与催化狄尔斯-阿尔德反应的反应速率的相关性

  摘要：

  各种甲硅烷基三氟甲磺酸酯的路易斯酸度通过使用 [D5] 吡啶作为 2H NMR 光谱探针进行量化。报道了吡啶-甲硅烷基加合物的 2 H NMR 信号的化学位移。三氟甲磺酸甲硅烷酯催化的 Diels-Alder 反应的速率常数是通过使用 UV/Vis 光谱确定的。观察到 2H NMR 化学位移的幅度与所研究的大多数甲硅烷基三氟甲磺酸酯的速率常数的相关性，但 Me3SiOTf 表现出惊人的大偏差。对照实验表明可以排除狄尔斯-阿尔德反应的质子催化。

  DOI：

  10.1002/ejoc.201101307

文献信息

• Ferrocene-Stabilized Silicon Cations as Catalysts for Diels–Alder Reactions: Attempted Experimental Quantification of Lewis Acidity and ReactIR Kinetic Analysis
  作者：Alexander R. Nödling、Kristine Müther、Volker H. G. Rohde、Gerhard Hilt、Martin Oestreich

  DOI：10.1021/om401040y

  日期：2014.1.13

  The Si-29 NMR chemical shifts of ferrocene-stabilized silicon cations span a wide range depending on the substituents at the silicon atom. These pronounced differences in deshielding of the silicon atom do not translate into significant differences in their catalytic activity in Diets-Alder reactions. It was shown by Lewis pair formation with Lewis base probes (Et3PO and pyridine-d(5)) that there is hardly any difference between these silicon cations after coordination to a Lewis base. This finding not only thwarts experimental quantification of the Lewis acidity of the free Lewis acids but also demonstrates that the reactivity differences are largely due to steric effects for a given counteranion. These observations are further verified by a ReactIR kinetic analysis. The Lewis acidity of silicon cations and their performance as catalysts cannot be correlated with Si-29 NMR chemical shifts as well as resonances of adducts with Lewis base probes, not even for a subset of silicon Lewis acids.