2,1,3-benzothiaselenazolium tetrachlorogallate | 1427783-81-0

• 英文名称: 2,1,3-benzothiaselenazolium tetrachlorogallate
• CAS: 1427783-81-0
• 化学式: C₆H₄NSSe*Cl₄Ga
• 分子量: 412.665
• InChiKey: DRPRYFNMTWBQRW-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  gallium(III) trichloride 、 2,1,3-benzothiaselenazolium chloride 以 乙腈 为溶剂， 反应 48.0h， 以58%的产率得到2,1,3-benzothiaselenazolium tetrachlorogallate
  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