1,2-bis(2,3-dimercaptobenzamido)ethane | 433288-07-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯硫酚类
• 英文名称: 1,2-bis(2,3-dimercaptobenzamido)ethane
• 英文别名: N-[2-[[2,3-bis(sulfanyl)benzoyl]amino]ethyl]-2,3-bis(sulfanyl)benzamide
• CAS: 433288-07-4
• 化学式: C₁₆H₁₆N₂O₂S₄
• 分子量: 396.579
• InChiKey: CRJBTTGWLBPHPW-UHFFFAOYSA-N

物化性质

• 沸点：
  623.4±55.0 °C(Predicted)
• 密度：
  1.408±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  24
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  62.2
• 氢给体数：
  6
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  [ReOCl₃(PPh₃)₂] 、 四苯基氯化膦 、 1,2-bis(2,3-dimercaptobenzamido)ethane 在 Na₂CO₃ 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以65%的产率得到[Ph4P]2[(ReO(1,2-bis(2,3-dimercaptobenzamido)ethane(-4H)))2]
  参考文献：
  名称：

  A Dinuclear Double‐Stranded Oxido Complex of Re ^V with a Bis(benzene‐ o ‐dithiolato) Ligand

  摘要：

  AbstractThe reaction of [ReOCl3(PPh3)2] with 1,2‐bis(2,3‐dimercaptobenzamido)ethane (H4‐1) in the presence of Na2CO3 in methanol under anaerobic conditions affords the dinuclear ReV oxido complex [PPh4]2[ReO(1)]2 containing two distorted square‐pyramidal {ReVOS4} units bridged by the ligand strands in a double‐stranded fashion. The coordinationgeometry around the metal centers is similar to the one observed for [ReO(bdt)2]–. The ReS4 planes are arranged in a coplanar fashion and are not twisted around the metal–metal vector, which prevents the complex to adopt a helical structure. Luminescence studies show the presence of emission bands, which are assigned to singlet‐singlet transitions exhibiting very fast decays (ca. 10 ns). Theoretical Density Functional (DFT) studies on geometry and electronic properties were performed employing the hybrid B3LYP and PBE1PBE functionals. While the general trends observed in the experimental data are well reproduced in all cases, a good agreement was obtained using PBE1PBE, in particular for the Re–S bonds. Natural Bond Orbitals (NBO) analysis indicates the presence of polarized Re≡O and Re–S bonds, both of them polarized toward the non‐metal. The calculation show that the molecular orbitals of the ReV are doubly degenerated, the occupied 5d orbital of rhenium lying beneath occupied sulfur‐based MOs due to the rigid geometry imposed by the C–C backbone of the bis(benzene‐o‐dithiolato) ligands. The origin of all absorption bands is ascribed to a ligand‐to‐metal charge transfer (LMCT), in which occupied sulfur‐based orbitals and unoccupied rhenium‐centered orbitals are involved.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

  DOI：

  10.1002/ejic.200900496
• 作为产物：
  描述：

  邻二氯苯 在 正丁基锂 、 氯化亚砜 、 萘 、 四甲基乙二胺 、 sodium 作用下， 以 四氢呋喃 、 正己烷 、 氯仿 、 N,N-二甲基甲酰胺 为溶剂， 反应 89.5h， 生成 1,2-bis(2,3-dimercaptobenzamido)ethane
  参考文献：
  名称：

  双（苯二硫代）配体的双核配合物。

  摘要：

  作为针对与苯二硫醇盐供体的螺旋配位化合物进行更广泛研究的一部分，我们合成了双（苯二硫醇）配体1,2-双（2,3-二巯基苯甲酰胺基）乙烷（H（4）-1）和1,2 -双（2,3-二巯基苯基）乙烷（H（4）-2）。两种配体均与Ni（II），Ni（III）形成双核络合物，并在空气氧化后在平衡条件下形成Co（III）离子。配合物（NEt（4））（4）[Ni（II）（2）（1）（2）]（11 b），（NEt（4））（2）[Ni（III）（2）（1） （2）]（13）和Na（4）[Ni（II）（2）（2）（2）]（14）通过X射线衍射表征。在所有络合物中，两个正方形平面的[Ni（S（2）C（6）H（3）R）（2）]单元通过碳骨架以双链方式连接，并且它们假定共平面排列像楼梯一样。循环伏安研究表明氧化还原电势对配体类型的强烈依赖性。镍上2（4-）的1（4-）取代（11b为-785 mV相对于二茂铁为14130

  DOI：

  10.1002/1521-3765(20020315)8:6<1327::aid-chem1327>3.0.co;2-n

文献信息

• Metallosupramolecular Chemistry with Bis(benzene-<i>o</i>-dithiolato) Ligands
  作者：Thorsten Kreickmann、Christian Diedrich、Tania Pape、Han Vinh Huynh、Stefan Grimme、F. Ekkehardt Hahn

  DOI：10.1021/ja063655u

  日期：2006.9.1

  enantiomerically pure chiral ligand 3(4)(-) shows a strong Cotton effect in the CD spectrum, indicating that the chirality of the ligands leads to the formation of chiral metal centers. The o-phenylene diamine bridged bis(benzene-o-dithiol) ligand H(4)-4 reacts with Ti(4+) to give the dinuclear double-stranded complex Li(2)[Ti(2)(4)(2)(mu-OCH(3))(2)] containing two bridging methoxy ligands between the metal centers

  双（苯-邻二硫醇）配体 H(4)-1、H(4)-2 和 H(4)-3 与 [Ti(OC(2)H(5))(4)] 反应生成给出双核三链螺旋 [Ti(2)L(3)](4)(-) (L = 1(4)(-), 2(4)(-), 3(4)(-))。核磁共振波谱研究表明，复杂的阴离子在溶液中具有 C(3) 对称性。(PNP)(4)[Ti(2)(2)(3)] ((PNP)(4)[14]) 的晶体结构分析证实了固态复合阴离子的 C(3) 对称性。Li(PNP)(3)[Ti(2)(1)(3)] (Li(PNP)(3)[13]) 中的复合阴离子在固态下不表现出 C(3) 对称性，因为锂桥接复合阴离子聚合物链的形成。复合物[13](4)(-)和[14](4)(-)作为Delta，Delta和Lambda，Lambda异构体的外消旋混合物获得。相比之下，配合物 (PNP)(4)[Ti(2)(3)(3)] ((PNP)(4)[15])
• A dinuclear triple-stranded helicate with a bis(benzene-o-dithiolato) ligand
  作者：F. Ekkehardt Hahn、Thorsten Kreickmann、Tania Pape

  DOI：10.1039/b514442f

  日期：——

  The bis(benzene-o-dithiol) ligand H4-1 reacts with Ti4+ in a self-assembly reaction to give the dinuclear triple-stranded helicate [Ti2(1)3]4- which is the first helicate build exclusively from benzene-o-dithiolato donor groups.

  双（苯-邻-二硫醇）配体H4-1在自组装反应中与Ti4 +反应，生成双核三链螺旋结构[Ti2（1）3] 4-，这是第一个完全由苯-o构筑的螺旋结构-dithiolato供体基团。
• Dinuclear Complexes with Bis(benzenedithiolate) Ligands
  作者：Han Vinh Huynh、Christian Schulze-Isfort、Wolfram W. Seidel、Thomas Lügger、Roland Fröhlich、Olga Kataeva、F. Ekkehardt Hahn

  DOI：10.1002/1521-3765(20020315)8:6<1327::aid-chem1327>3.0.co;2-n

  日期：2002.3.15

  of 1(4-) for 2(4-) on nickel (-785 mV for 11 b versus -1130 mV for 14, relative to ferrocene) affects the redox potential to a similar degree as the substitution of nickel for cobalt (-1160 mV for [Co(2)(1)(2)](2-)/[Co(2)(1)(2)](4-), relative to ferrocene). The redox waves display a markedly less reversible behavior for complexes with the shorter bridged ligand 2(4-) compared to those of 1(4-).

  作为针对与苯二硫醇盐供体的螺旋配位化合物进行更广泛研究的一部分，我们合成了双（苯二硫醇）配体1,2-双（2,3-二巯基苯甲酰胺基）乙烷（H（4）-1）和1,2 -双（2,3-二巯基苯基）乙烷（H（4）-2）。两种配体均与Ni（II），Ni（III）形成双核络合物，并在空气氧化后在平衡条件下形成Co（III）离子。配合物（NEt（4））（4）[Ni（II）（2）（1）（2）]（11 b），（NEt（4））（2）[Ni（III）（2）（1） （2）]（13）和Na（4）[Ni（II）（2）（2）（2）]（14）通过X射线衍射表征。在所有络合物中，两个正方形平面的[Ni（S（2）C（6）H（3）R）（2）]单元通过碳骨架以双链方式连接，并且它们假定共平面排列像楼梯一样。循环伏安研究表明氧化还原电势对配体类型的强烈依赖性。镍上2（4-）的1（4-）取代（11b为-785 mV相对于二茂铁为14130
• A Dinuclear Double‐Stranded Oxido Complex of Re ^V with a Bis(benzene‐ <i>o</i> ‐dithiolato) Ligand
  作者：Jorge S. Gancheff、Rodrigo Q. Albuquerque、Andrés Guerrero‐Martínez、Tania Pape、Luisa De Cola、F. Ekkehardt Hahn

  DOI：10.1002/ejic.200900496

  日期：2009.9

  AbstractThe reaction of [ReOCl3(PPh3)2] with 1,2‐bis(2,3‐dimercaptobenzamido)ethane (H4‐1) in the presence of Na2CO3 in methanol under anaerobic conditions affords the dinuclear ReV oxido complex [PPh4]2[ReO(1)]2 containing two distorted square‐pyramidal ReVOS4} units bridged by the ligand strands in a double‐stranded fashion. The coordinationgeometry around the metal centers is similar to the one observed for [ReO(bdt)2]–. The ReS4 planes are arranged in a coplanar fashion and are not twisted around the metal–metal vector, which prevents the complex to adopt a helical structure. Luminescence studies show the presence of emission bands, which are assigned to singlet‐singlet transitions exhibiting very fast decays (ca. 10 ns). Theoretical Density Functional (DFT) studies on geometry and electronic properties were performed employing the hybrid B3LYP and PBE1PBE functionals. While the general trends observed in the experimental data are well reproduced in all cases, a good agreement was obtained using PBE1PBE, in particular for the Re–S bonds. Natural Bond Orbitals (NBO) analysis indicates the presence of polarized Re≡O and Re–S bonds, both of them polarized toward the non‐metal. The calculation show that the molecular orbitals of the ReV are doubly degenerated, the occupied 5d orbital of rhenium lying beneath occupied sulfur‐based MOs due to the rigid geometry imposed by the C–C backbone of the bis(benzene‐o‐dithiolato) ligands. The origin of all absorption bands is ascribed to a ligand‐to‐metal charge transfer (LMCT), in which occupied sulfur‐based orbitals and unoccupied rhenium‐centered orbitals are involved.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)