3H-benzo[1,2,3]thiaselenazolium chloride | 61712-91-2

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: 3H-benzo[1,2,3]thiaselenazolium chloride
• 英文别名: benzo[1,2,3]thiaselenazolylium; chloride；Benzo-1,2,3-thiaselenazolium；1,2,3-Benzothiaselenazol-2-ium chloride；1,2,3-benzothiaselenazol-1-ium;chloride
• CAS: 61712-91-2
• 化学式: C₆H₄NSSe*Cl
• 分子量: 236.583
• InChiKey: FTBMTZIIRSMFMZ-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -1.36
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  41.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3H-benzo[1,2,3]thiaselenazolium chloride 在 三苯基锑 作用下， 以 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  Experimental and Computational Study on the Structure and Properties of Herz Cations and Radicals: 1,2,3-Benzodithiazolium, 1,2,3-Benzodithiazolyl, and Their Se Congeners

  摘要：

  Salts of 1,2,3-benzodithiazolium (1), 2,1,3-benzothiaselenazolium (3), and 1,2,3-benzodiselenazolium (4) (Herz cations), namely, [1][BF4], [1][SbCl6], [3][BF4], [3][GaCl4], [3][SbCl6], and [4][GaCl4], were prepared from the corresponding chlorides and NaBF4, GaCl3, or SbCl5. It was found that [1][SbCl6] and [3][SbCl6] spontaneously transform in MeCN solution to [1](3)[SbCl6](2)[0] and [3](3)[SbCl6](2)[Cl], respectively. [1][BF4], [1](3)[SbCl6](2)[Cl], [3][BF4], [3](3)[SbCl6](2)[Cl], and [4]-[GaCl4] were structurally characterized by X-ray diffraction (XRD). In solution, these [BF4](-) and [GaCl4](-) salts as well as [1][GaCl4], [2][GaCl4], [3][GaCl4], [3][Cl], and [4][Cl] were characterized by multinuclear nuclear magnetic resonance (NMR). The corresponding Hen radicals 1(center dot)-4(center dot) were obtained in toluene and DCM solutions by the reduction of the appropriate salts with Ph3Sb and characterized by EPR. Cations 1-4 and radicals 1(center dot)-4(center dot) were investigated computationally at the density functional theory (DFT) and second-order Moller-Plesset (MP2) levels of theory. The B1B95/cc-pVTZ method was found to satisfactorily reproduce the experimental geometries of 1-4; an increase in the basis set size to cc-pVQZ results in only minor changes. For both 1-4 and 1(center dot)-4(center dot), the Hirshfeld charges and bond orders, as well as the Hirshfeld spin densities for the radicals, were calculated using the B IB95/cc-pVQZ method. It was found for both the cations and the radicals that replacing S atoms with Se atoms leads to considerable changes in the atomic charges, bond lengths, and bond orders only at the involved and the neighboring sites. According to the calculations, 60% of the positive charge in the cations and 80% of the spin density in the radicals is localized on the heterocycles, with the spin density distributions being very similar for all radicals 1(center dot)-4(center dot). For the cations 1-4, the NICS values (B3LYP/cc-pVTZ for B1B95/cc-pVTZ geometries) lie in the narrow range from -5.5 ppm to -6.6 ppm for the carbocycles, and from -14.4 ppm to -15.5 ppm for heterocycles, clearly indicating the aromaticity of the cations. Calculations on radical dimers [1(center dot)](2)-[4(center dot)](2) revealed, with only one exception, positive dimerization energies, i.e., the dimers are inherently unstable in the gas phase.

  DOI：

  10.1021/ic302203t
• 作为产物：
  描述：

  1,2,3-benzodithiazolium chloride 在 硒脲酸 、 溶剂黄146 作用下， 以 乙醇 为溶剂， 生成 3H-benzo[1,2,3]thiaselenazolium chloride
  参考文献：
  名称：

  苯并1,2,3-硫代噻唑鎓盐的合成及某些性质

  摘要：

  DOI：

  10.1007/bf00945597

文献信息

• Heavy Atom Analogues of 1,2,3-Dithiazolylium Salts: Preparation, Structures and Redox Chemistry
  作者：Maarit Risto、Abdeljalil Assoud、Stephen M. Winter、Raija Oilunkaniemi、Risto S. Laitinen、Richard T. Oakley

  DOI：10.1021/ic8013738

  日期：2008.11.3

  Lewis acid adduct at nitrogen. Reduction of the benzo cations [2a,b](+) affords the respective radicals 2a,b, both of which have been characterized by electron paramagnetic resonance (EPR) spectroscopy. Attempts to generate the corresponding radical 2c have been unsuccessful, although a material of nominally correct elemental composition can be generated by chemical reduction. The energetics of association

  描述了合成苯并[1,2,3]硫代噻唑基阳离子[2c]（+）及其硒类似物[2b]（+）的途径。进入阳离子框架涉及N，N，S-三甲硅烷基化的2-氨基苯硫醇的中介。后者与硒和碲化碲ECl4（E = Se，Te）平稳反应，得到所需的杂环苯甲酸阳离子[2b]（+）和[2c]（+），为它们的氯化物盐。阴离子交换提供了[2c]（+）的相应的GaCl4（-），OTf（-）和TECl5（-）盐，所有这些盐均已通过X射线晶体学表征。硫和硒阳离子[2a]（+）和[2b]（+）的没食子酸盐以离子对阳离子和阴离子的形式结晶，而[2c]（+）的盐则采用固态结构，显示出强烈的缔合作用。通过短的分子间Te-N'键形成阳离子。然而，在GaCl3存在下，二氯乙烷中[2c]（+）盐的结晶会导致二聚体裂解，并在氮原子上形成路易斯酸加合物。苯并阳离子[2a，b]（+）的还原得到相应的自由基2a，b，这两个自由基均已通过电子顺磁共振