1-(adamantan-1-yl-2,2,8,8,9,9-d₆)-3-(2,4,6-trimethylphenyl)-4,5-dihydro-1H-imidazol-3-iumchloride | 1600534-81-3

• 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: 1-(adamantan-1-yl-2,2,8,8,9,9-d₆)-3-(2,4,6-trimethylphenyl)-4,5-dihydro-1H-imidazol-3-iumchloride
• CAS: 1600534-81-3
• 化学式: C₂₂H₃₁N₂*Cl
• 分子量: 364.907
• InChiKey: MJOMRTQWLPXDJQ-LMHBMPQTSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  1.57
• 重原子数：
  25.0
• 可旋转键数：
  2.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  6.25
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  1-(adamantan-1-yl-2,2,8,8,9,9-d₆)-3-(2,4,6-trimethylphenyl)-4,5-dihydro-1H-imidazol-3-iumchloride 在 potassium 2-methylbutan-2-olate 作用下， 以 正己烷 、 苯 为溶剂， 反应 24.0h， 生成 (1-(adamant-1-yl-2,2,8,8,9,9-d₆)-3-(2,4,6-trimethylphenyl)-2-imidazolidinylidene)bistriflato(o-isopropoxyphenylmethylidene)ruthenium
  参考文献：
  名称：

  Carboxylate-Assisted C(sp³)–H Activation in Olefin Metathesis-Relevant Ruthenium Complexes

  摘要：

  The mechanism of C H activation at metathesis-relevant ruthenium(II) benzylidene complexes was studied both experimentally and computationally. Synthesis of a ruthenium dicarboxylate at a low temperature allowed for direct observation of the C H activation step, independent of the initial anionic ligand-exchange reactions. A first-order reaction supports an intramolecular concerted metalation-deprotonation mechanism with Delta G(298K)double dagger = 22.2 +/- 0.1 kcal.mol(-1) for the parent N-adamantyl-N'-mesityl complex. An experimentally determined Delta S double dagger = 5.2 +/- 2.6 eu supports a highly ordered transition state for carboxylate-assisted C(sp(3))-H activation. Experimental results, including measurement of a large primary kinetic isotope effect (k(H)/k(D) = 8.1 +/- 1.7), agree closely with a computed six-membered carboxylate-assisted C H activation mechanism where the deprotonating carboxylate adopts a pseudo-apical geometry, displacing the aryl ether chelate. The rate of cyclometalation was found to be influenced by both the electronics of the assisting carboxylate and the ruthenium ligand environment.

  DOI：

  10.1021/ja5021958
• 作为产物：
  描述：

  在 盐酸 作用下， 以 乙醚 为溶剂， 反应 1.13h， 生成 1-(adamantan-1-yl-2,2,8,8,9,9-d₆)-3-(2,4,6-trimethylphenyl)-4,5-dihydro-1H-imidazol-3-iumchloride
  参考文献：
  名称：

  Carboxylate-Assisted C(sp³)–H Activation in Olefin Metathesis-Relevant Ruthenium Complexes

  摘要：

  The mechanism of C H activation at metathesis-relevant ruthenium(II) benzylidene complexes was studied both experimentally and computationally. Synthesis of a ruthenium dicarboxylate at a low temperature allowed for direct observation of the C H activation step, independent of the initial anionic ligand-exchange reactions. A first-order reaction supports an intramolecular concerted metalation-deprotonation mechanism with Delta G(298K)double dagger = 22.2 +/- 0.1 kcal.mol(-1) for the parent N-adamantyl-N'-mesityl complex. An experimentally determined Delta S double dagger = 5.2 +/- 2.6 eu supports a highly ordered transition state for carboxylate-assisted C(sp(3))-H activation. Experimental results, including measurement of a large primary kinetic isotope effect (k(H)/k(D) = 8.1 +/- 1.7), agree closely with a computed six-membered carboxylate-assisted C H activation mechanism where the deprotonating carboxylate adopts a pseudo-apical geometry, displacing the aryl ether chelate. The rate of cyclometalation was found to be influenced by both the electronics of the assisting carboxylate and the ruthenium ligand environment.

  DOI：

  10.1021/ja5021958