4,5-diCl IMD salt | 509077-78-5

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 芳基卤化物
• 英文名称: 4,5-diCl IMD salt
• 英文别名: 4,5-dichloro-1,3-dimethyl-1H-imidazol-3-ium iodide；1,3-dimethyl-4,5-dichloro-imidazolium iodide；1,3-dimethyl-4,5-dichloroimidazolium iodide；4,5-dichloro-1,3-dimethylimidazolium iodide；[Cl2C3HN2(Me)2]I
• CAS: 509077-78-5
• 化学式: C₅H₇Cl₂N₂*I
• 分子量: 292.934
• InChiKey: QJBHJDYOIGBKGR-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -1.84
• 重原子数：
  10.0
• 可旋转键数：
  0.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  8.81
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  4,5-diCl IMD salt 在 sodium hydride 、 caesium carbonate 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 生成 1,3-dimethyl-4,5-dichloroimidazolylidene dimer
  参考文献：
  名称：

  N-Heterocyclic Carbenes as Reversible Exciton-Delocalizing Ligands for Photoluminescent Quantum Dots

  摘要：

  Delocalization of excitons within semiconductor quantum dots (QDs) into states at the interface of the inorganic core and organic ligand shell by so-called "exciton-delocalizing ligands (EDLs)" is a promising strategy to enhance coupling of QD excitons with proximate molecules, ions, or other QDs. EDLs thereby enable enhanced rates of charge carrier extraction from, and transport among, QDs and dynamic colorimetric sensing. The application of reported EDLs-which bind to the QDs through thiolates or dithiocarbamates-is however limited by the irreversibility of their binding and their low oxidation potentials, which lead to a high yield of photoluminescence-quenching hole trapping on the EDL. This article describes a new class of EDLs for QDs, 1,3-dimethyl-4,5-disubstituted imidazolylidene N-heterocyclic carbenes (NHCs), where the 4,5-substituents are Me, H, or Cl. Postsynthetic ligand exchange of native oleate capping ligands for NHCs results in a bathochromic shift of the optical band gap of CdSe QDs (R = 1.17 nm) of up to 111 meV while the colloidal stability of the QDs is maintained. This shift is reversible for the MeNHC-capped and HNHC-capped QDs upon protonation of the NHC. The magnitude of exciton delocalization induced by the NHC (after scaling for surface coverage) increases with the increasing acidity of its pi system, which depends on the substituent in the 4,5-positions of the imidazolylidene. The NHC-capped QDs maintain photoluminescence quantum yields of up to 4.2 +/- 1.8% for shifts of the optical band gap as large as 106 meV.

  DOI：

  10.1021/jacs.9b13605
• 作为产物：
  描述：

  4,5-二氯咪唑 、 碘甲烷 在 potassium carbonate 作用下， 以 乙腈 为溶剂， 反应 72.0h， 生成 4,5-diCl IMD salt
  参考文献：
  名称：

  N-Heterocyclic Carbenes as Reversible Exciton-Delocalizing Ligands for Photoluminescent Quantum Dots

  摘要：

  Delocalization of excitons within semiconductor quantum dots (QDs) into states at the interface of the inorganic core and organic ligand shell by so-called "exciton-delocalizing ligands (EDLs)" is a promising strategy to enhance coupling of QD excitons with proximate molecules, ions, or other QDs. EDLs thereby enable enhanced rates of charge carrier extraction from, and transport among, QDs and dynamic colorimetric sensing. The application of reported EDLs-which bind to the QDs through thiolates or dithiocarbamates-is however limited by the irreversibility of their binding and their low oxidation potentials, which lead to a high yield of photoluminescence-quenching hole trapping on the EDL. This article describes a new class of EDLs for QDs, 1,3-dimethyl-4,5-disubstituted imidazolylidene N-heterocyclic carbenes (NHCs), where the 4,5-substituents are Me, H, or Cl. Postsynthetic ligand exchange of native oleate capping ligands for NHCs results in a bathochromic shift of the optical band gap of CdSe QDs (R = 1.17 nm) of up to 111 meV while the colloidal stability of the QDs is maintained. This shift is reversible for the MeNHC-capped and HNHC-capped QDs upon protonation of the NHC. The magnitude of exciton delocalization induced by the NHC (after scaling for surface coverage) increases with the increasing acidity of its pi system, which depends on the substituent in the 4,5-positions of the imidazolylidene. The NHC-capped QDs maintain photoluminescence quantum yields of up to 4.2 +/- 1.8% for shifts of the optical band gap as large as 106 meV.

  DOI：

  10.1021/jacs.9b13605

文献信息

• [(NHC)(NHCewg)RuCl2(CHPh)] Complexes with Modified NHCewg Ligands for Efficient Ring-Closing Metathesis Leading to Tetrasubstituted Olefins
  作者：Volodymyr Sashuk、Lars H. Peeck、Herbert Plenio

  DOI：10.1002/chem.200903275

  日期：2010.4.6

  yield from the ruthenium precursor. To learn which one of the two NHC ligands acts as the leaving group in olefin metathesis reactions two complexes, [(FL‐NHC)(NHCewg)RuCl2(CHPh)] and [(FL‐NHCewg)(NHC)RuCl2(CHPh)], with a dansyl fluorophore (FL)‐tagged electron‐rich NHC ligand (FL‐NHC) and an electron‐deficient NHC ligand (FL‐NHCewg) were prepared. The fluorescence of the dansyl fluorophore is quenched

  咪唑鎓盐（NHC EWG ⋅ HCl中）与在4,5位上的电子可变取代基（H，H或Cl，Cl或H，NO 2或CN，CN）和位可变取代基的1,3-位（ME ，Me或Et，Et或i Pr，i Pr或Me，i Pr）被合成并转化为各自的[AgI（NHC）ewg ]配合物。[（NHC）RuCl 2（CHPh）（py）2 ]与[AgI（NHC ewg）]配合物的反应提供了各自的[（NHC）（NHC ewg）RuCl 2（CHPh）]络合物，收率极高。研究了此类络合物在开环复分解（RCM）反应中产生四取代烯烃的催化活性。为了获得定量的底物转化率，催化剂在80°C下甲苯中的催化剂负载量为0.2–0.5 mol％就足够了。在此类RCM反应中具有最佳催化活性和最快引发速率的配合物具有NHC ewg基团，该基团带有1,3-Me，i Pr和4,5-Cl，Cl取代基，可以从该化合物中以95％的分离产率合成钌前体。要
• Borylfuroxans: Synthesis and Applications
  作者：Weibin Xie、Masahiko Hayashi、Ryosuke Matsubara

  DOI：10.1021/acs.orglett.1c01250

  日期：2021.6.4

  Herein we report the first synthesis of borylfuroxans via the reaction of sulfonylfuroxans with Lewis base-ligated boranes under radical conditions. As a synthetic application, the transformation of borylfuroxans to a range of 1,2-dioximes and their derivatives is demonstrated.

  在这里，我们报告了通过磺酰呋喃与路易斯碱连接的硼烷在自由基条件下反应的首次合成。作为合成应用，展示了硼基呋喃转化为一系列 1,2-二肟及其衍生物的过程。
• A comparative study on NHC-functionalized ternary Se/Te–Fe–Cu compounds: synthesis, catalysis, and the effect of chalcogens
  作者：Minghuey Shieh、Yu-Hsin Liu、Chih-Chin Wang、Si-Huan Jian、Chien-Nan Lin、Yen-Ming Chen、Chung-Yi Huang

  DOI：10.1039/c9nj02051a

  日期：——

  of N-heterocyclic carbene (NHC)-incorporated Se–Fe–Cu compounds, bis-1,3-dimethylimidazol-2-ylidene (bis-Me2-imy)-containing compound [(μ4-Se)Fe3(CO)9Cu(Me2-imy)}2] (2), bis-N-methyl- or bis-N-isopropyl-substituted benzimidazol-2-ylidene (bis-Me2-bimy or bis-iPr2-bimy)-incorporated compounds [(μ4-Se)Fe3(CO)9Cu(Me2-bimy)}2] (3) or [(μ4-Se)Fe3(CO)9Cu(iPr2-bimy)}2] (4), and a bis-1,3-dimethyl-4,5-di

  N-杂环卡宾的新家族（NHC）-incorporated硒-铁-铜化合物，双-1,3-二甲基咪唑-2-亚基（双-ME 2 -imy）含化合物[（μ 4 -Se）的Fe 3（CO）9 Cu（Me 2 -imy）} 2 ]（2），双-N-甲基或双-N-异丙基取代的苯并咪唑-2-亚烷基（双-Me 2-双甲基或双-i PR 2 -bimy）-incorporated化合物[（μ 4 -Se）的Fe 3（CO）9 铜（ME 2 -bimy）} 2 ]（3）或[（μ 4-Se）的Fe 3（CO）9 铜（我镨2 -bimy）} 2 ]（4），和双-1,3-二甲基-4,5- dichloroimidazol -2-亚基（双-ME 2 - CL 2 -imy）含化合物[（μ 3 -Se）的Fe 3（CO）9 铜（ME 2 -Cl 2 -imy）} 2 ]（5）所示，在轻便一锅反应中等产率，合成三元预先设计的化合物[（μ
• Synthesis and anticancer properties of gold(I) and silver(I) N-heterocyclic carbene complexes
  作者：Tammy J. Siciliano、Michael C. Deblock、Khadijah M. Hindi、Semih Durmus、Matthew J. Panzner、Claire A. Tessier、Wiley J. Youngs

  DOI：10.1016/j.jorganchem.2010.10.054

  日期：2011.3

  lver(I) nitrate and bis(4,5-dichloro-1,3-dimethylimidazol-2-ylidene)silver(I) nitrate were prepared by reacting the corresponding imidazolium nitrate salts with silver oxide. Bis(1,3-dimethylimidazol-2-ylidene)gold(I) nitrate and bis(4,5-dichloro-1,3-dimethylimidazol-2-ylidene)gold(I) nitrate salts were prepared via transmetallation of their silver precursors with chloro dimethylsulfide gold. The anticancer

  通过使相应的咪唑鎓硝酸盐反应制得硝酸双（1,3-二甲基咪唑-2-亚基）银（I）和硝酸双（4,5-二氯-1,3-二甲基咪唑-2-亚基）银（I）与氧化银。硝酸双（1,3-二甲基咪唑-2-亚基）金（I）和硝酸银双（4,5-二氯-1,3-二甲基咪唑-2-亚基）金（I）盐通过其银前体的金属转移制备含氯二甲基硫金。使用NCI-H460肺癌细胞测定抗癌特性。通过将金和银化合物与顺铂进行比较来确定功效。
• Carbene Complexes Made Easily: Decomposition of Reissert Compounds and Further Synthetic Approaches
  作者：Agnes Bittermann、Denys Baskakov、Wolfgang A. Herrmann

  DOI：10.1021/om900354v

  日期：2009.9.14

  New methods for the preparation of NHC-metal complexes have been developed. It was shown that a nitrile group in Reissert analogous compounds can act as a good leaving group in thermal elimination, resulting in carbene formation. Moreover potassium carbonate was introduced as a highly efficient and mild reagent for the generation of N-heterocyclic carbene complexes in good to excellent yields, even

  已经开发了用于制备NHC-金属配合物的新方法。结果表明，Reissert类似化合物中的腈基可在热消除中充当良好的离去基团，从而形成卡宾。此外，引入碳酸钾作为一种高效温和的试剂，即使在水中也能以极高的产率获得N-杂环卡宾络合物，这是最环保的介质。