(ImidNHC-Mes)*H | 1353038-87-5

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: (ImidNHC-Mes)*H
• 英文别名: 2,4-dioxo-1,5-dimesityl-1,3,5-triazinan-1-ium-3-ide
• CAS: 1353038-87-5
• 化学式: C₂₁H₂₃N₃O₂
• 分子量: 349.433
• InChiKey: SFDOIRWTCOSQQX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.28
• 重原子数：
  26.0
• 可旋转键数：
  2.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  57.05
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (ImidNHC-Mes)*H 在 双(三甲基硅烷基)氨基钾 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 0.33h， 以100%的产率得到potassium 2,4-dioxo-1,5-dimesityl-1,3,5-triazinan-6-ylidene-3-ide
  参考文献：
  名称：

  一种基于融合碳和Imidato功能的准确Janus型配体系统

  摘要：

  新的阴离子杂环 亚胺NHC（4,6-二氧代-1,3,5-三嗪-二亚甲基-5-化物）结合了卡宾和阴离子亚氨酸酯，可通过1,3-之间的偶合反应制备将二甲烯丙基甲form和N-苯氧基羰基异氰酸酯进行去质子化。确定了这种可切换配体的供体性质，而其歧义性质是通过异型堆叠多金属结构的定向构建而建立的。

  DOI：

  10.1002/chem.201102767
• 作为产物：
  描述：

  N,N'-dimesitylformamidine 、 异氰酸基甲酸苯酯 在 正丁基锂 、 三甲基氯硅烷 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 0.33h， 以83%的产率得到(ImidNHC-Mes)*H
  参考文献：
  名称：

  一种基于融合碳和Imidato功能的准确Janus型配体系统

  摘要：

  新的阴离子杂环 亚胺NHC（4,6-二氧代-1,3,5-三嗪-二亚甲基-5-化物）结合了卡宾和阴离子亚氨酸酯，可通过1,3-之间的偶合反应制备将二甲烯丙基甲form和N-苯氧基羰基异氰酸酯进行去质子化。确定了这种可切换配体的供体性质，而其歧义性质是通过异型堆叠多金属结构的定向构建而建立的。

  DOI：

  10.1002/chem.201102767

文献信息

• (Cyclopentadienyl)iron(II) Complexes of N-Heterocyclic Carbenes Bearing a Malonate or Imidate Backbone: Synthesis, Structure, and Catalytic Potential in Hydrosilylation
  作者：Vincent César、Luis C. Misal Castro、Thomas Dombray、Jean-Baptiste Sortais、Christophe Darcel、Stéphane Labat、Karinne Miqueu、Jean-Marc Sotiropoulos、Rémy Brousses、Noël Lugan、Guy Lavigne

  DOI：10.1021/om400625q

  日期：2013.8.26

  The backbone-functionalized anionic carbenes maloNHC (1(R); malonate backbone) and imidNHC (2; imidate backbone) were generated in situ from their respective zwitterionic precursors and treated with FeCp(CO)(2)I to afford the zwitterionic complexes FeCp(CO)(2)(1(R))} (3R; 5984% yield), and FeCp(CO)(2)(2)} (4; 77% yield), respectively. Methylation of the malonate complex 3Me takes place at one of the backbone oxygen atoms to give the cationic adduct [FeCp(CO)(2)(1MeMe)](OTf) ([5(Me)](OTf); 96% yield), whereas methylation of 4 takes place at the imidate nitrogen atom to produce the cationic adduct [FeCp(CO)(2)(2(Me))](OTf) ([6(Me)](OTf); 84% yield). All of the complexes were characterized by NMR and IR in solution, while X-ray structure analyses were carried out for 3(Me), 4, and [6(Me)](OTf). In addition, a detailed experimental and theoretical investigation of the electron density within the archetypal zwitterionic complex 3Me was carried out. The observation of short intramolecular contacts between Cipso or Cortho of the mesityl groups of the carbene and the proximal carbonyl groups is rationalized in terms of a noncovalent through space pi-pi* interaction involving a two-electron delocalization of the occupied pi(Cipso pi Cortho) molecular orbital (MO) of the aryl ring into one vacant pi*(C pi O) MO of the carbonyl ligand. A theoretical analysis carried out on dissymmetrical model complexes reveals that the magnitude of such an interaction is correlated with the donor properties of aryl group substituents. A catalyst screening of the above complexes in the hydrosilylation of benzaldehyde under visible light irradiation revealed a dramatic effect of the electronic donor properties of these carbenes on the performances of their complexes, with the more nucleophilic carbene 1tBu in the zwitterionic species 3tBu appearing as the most efficient. This complex shows good efficiency and excellent chemoselectivity in the hydrosilylation of various aldehydes bearing reactive functional groups. It is also moderately active in the hydrosilylation of a few ketone substrates and exhibits very good performance in the hydrosilylation of representative aldimines and ketimines.