bis(2-methanethio-p-tolyl)amine | 1421946-27-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯硫酚类
• 英文名称: bis(2-methanethio-p-tolyl)amine
• 英文别名: bis(2-mercapto-p-tolyl)amine；bis(2-mercapto-4-methylphenyl)amine；5-Methyl-2-(4-methyl-2-sulfanylanilino)benzenethiol；5-methyl-2-(4-methyl-2-sulfanylanilino)benzenethiol
• CAS: 1421946-27-1
• 化学式: C₁₄H₁₅NS₂
• 分子量: 261.412
• InChiKey: ATAHJJJMWLEFPZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  14
• 氢给体数：
  3
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  二氯化双(三环己基膦)镍(II) 、 bis(2-methanethio-p-tolyl)amine 在 三乙胺 作用下， 以 甲苯 为溶剂， 反应 0.5h， 以51%的产率得到
  参考文献：
  名称：

  Hydrogen-Atom Noninnocence of a Tridentate [SNS] Pincer Ligand

  摘要：

  Double deprotonation of bis(2-mercapto-4-methylphenyl)amine ([SNS]H-3) followed by addition to NiCl2(PR3)(2) in air-free conditions afforded [SN(H)S]Ni(PR3) (1a, R = Cy; 1b, R = Ph) complexes, characterized as diamagnetic, square-planar nickel(II) complexes. When the same reaction was conducted with 3 equiv of KH, the diamagnetic anions K{[SNS]Ni(PR3)} were obtained (K[2a], R = Cy; K[2b], R = Ph). In the presence of air, the reaction proceeds with a concomitant one-electron oxidation. When R = Cy, a square-planar, S = 1/2 complex, [SNS]Ni(PCy3) (3a), was isolated. When R = Ph, the bimetallic complex {[SNS]Ni(PPh3)}(2) ({3b}(2)) was obtained. This bimetallic species is diamagnetic; however, in solution it dissociates to give S = 1/2 monomers analogous to 3a. Complexes 1-3 represent a hydrogen-atom-transfer series. The bond dissociation free energies (BDFEs) for 1a and 1b were calculated to be 63.9 +/- 0.1 and 62.4 +/- 0.2 kcal mol(-1), respectively, using the corresponding pK(a) and E degrees' values. Consistent with these BDFE values, TEMPO center dot reacted with la and 1b, resulting in the abstraction of a hydrogen atom to afford 3a and 3b, respectively.

  DOI：

  10.1021/acs.inorgchem.8b00618
• 作为产物：
  描述：

  N-benzyl-bis(2-methanethio-p-tolyl)amine 在 sodium 作用下， 以 氨 为溶剂， 以92%的产率得到bis(2-methanethio-p-tolyl)amine
  参考文献：
  名称：

  Synthesis and Characterization of a Redox-Active Bis(thiophenolato)amide Ligand, [SNS]^3–, and the Homoleptic Tungsten Complexes, W[SNS]₂ and W[ONO]₂

  摘要：

  A new tridentate redox-active ligand platform, derived from bis(2-mercapto-p-toly)amine, [SNScat]H-3, has been prepared in high yields by a four-step procedure starting from commericially available bis(p-tolyl)amine. The redox-active pincer-type ligand has been coordinated to tungsten to afford the six-coordinate, homoleptic complex W[SNS](2). To benchmark the redox behavior of the [SNS] ligand, the analogous tungsten complex of the well-known redox-active bis(3,5-di-tert-butylphenolato)amide ligand, W[ONO](2), also has been prepared. Both complexes show two reversible reductions and two partially reversible oxidations. Structural, spectroscopic, and electrochemical data all indicate that W[ONO](2) is best described as a tungsten(VI) metal center coordinated to two [ONOcat](3-) ligands. In contrast, experimental data suggests a higher degree of S -> W pi donation, giving the W[SNS](2) complex non-innocent electronic character that can be described as a tungsten(IV) metal center coordinated to two [SNSsq](2-) ligands.

  DOI：

  10.1021/ic302506e

文献信息

• Metal-Ion Influence on Ligand-Centered Hydrogen-Atom Transfer
  作者：Bronte J. Charette、Joseph W. Ziller、Alan F. Heyduk

  DOI：10.1021/acs.inorgchem.0c02981

  日期：2021.2.1

  complexes containing a tridentate pincer ligand derived from bis(2-mercapto-p-tolyl)amine, [SNS]H3. Six new metal complexes of palladium and platinum were synthesized with the [SNS] ligand platform in different redox and protonation states to complete the group 10 series previously reported with nickel. The HAT reactivity was examined for this family of nickel, palladium, and platinum complexes to determine

  对于包含衍生自双（2-巯基-对甲苯基）胺[SNS] H 3的三齿钳状配体的第10族金属配合物家族，检查了以配体为中心的氢原子转移（HAT）反应性。使用[SNS]配体平台以不同的氧化还原和质子化状态合成了六种新的钯和铂金属配合物，以完成先前报道的镍第10组。检查了镍，钯和铂配合物这一家族的HAT反应性，以确定金属离子对以配体为中心的反应性的影响。热力学测量表明，NH键解离自由能增加了大约10 kcal mol –1Ni
• Heterobimetallic and Heterotrimetallic Clusters Containing a Redox‐Active Metalloligand
  作者：M. K. Wojnar、Joseph W. Ziller、Alan F. Heyduk

  DOI：10.1002/ejic.201701222

  日期：2017.12.22

  A new multimetallic construct has been developed utilizing a redox‐active metalloligand. The molybdenum complex, Mo[SNS]2 1; [SNS]H3 = bis(2‐mercapto‐p‐tolyl)amine}, has been shown to coordinate to Ni(dppe) dppe = 1,2‐bis(diphenylphosphanyl)ethane} through two cis thiolate donors to generate heterobimetallic Mo[SNS]2Ni(dppe) (2) and heterotrimetallic Mo[SNS]2Ni(dppe)}2 (3). X‐ray diffraction studies

  利用氧化还原活性金属配体开发了一种新的多金属结构。钼配合物Mo [SNS] 2 1 ; [SNS] H 3 =双（2-巯基对甲苯基胺）}已显示通过两个顺式硫醇盐供体与Ni（dppe）dppe = 1,2-双（二苯基膦基）乙烷}配位生成异双金属Mo [SNS] 2 Ni（dppe）（2）和异三金属Mo [SNS] 2 Ni（dppe）} 2（3）。X射线衍射研究证实了固态的钼和镍中心之间存在正式的金属键。但是，NMR光谱研究表明，簇内相互作用在溶液中是动态的。Mo [SNS] 2金属配体在2和3中产生了丰富的氧化还原化学，而在后一种情况下，电化学和光谱数据表明，尽管存在金属与金属的键合网络，3 +是一种局部化合价络合物。
• Two-Electron Mixed Valency in a Heterotrimetallic Nickel–Vanadium–Nickel Complex
  作者：Michael K. Wojnar、Joseph W. Ziller、Alan F. Heyduk

  DOI：10.1021/acs.inorgchem.2c03381

  日期：2023.1.30

  [V(SNS)2Ni(dppe)}2]−, with V–Ni bond lengths of 2.78 and 2.79 Å. One-electron oxidation of monoanionic [V(SNS)2Ni(dppe)}2]− yielded neutral, paramagnetic V(SNS)2Ni(dppe)}2. The solid-state structure of V(SNS)2Ni(dppe)}2 revealed that the two nickel ions occupy unique coordination environments: one nickel is in a square-planar S2P2 coordination environment (τ4 = 0.19), with a long Ni···V distance of 3.45 Å; the other

  混合价配合物代表了一类诱人的配位化合物，用于研究限制在分子框架内的电子转移。在螯合金属配体 [ V ( SNS ) 2 ] − [ dppe = bis (二苯基膦）乙烷；(SNS) 3– = 双 (2-thiolato-4-甲基苯基) 酰胺]。钒镍键跨越 [V(SNS) 2 Ni(dppe)} 2 ] −结构中的异三金属核，V-Ni 键长分别为 2.78 和 2.79 Å。单阴离子[V(SNS)的单电子氧化2 Ni(dppe)} 2 ] -产生中性顺磁性 V(SNS) 2 Ni(dppe)} 2。V(SNS) 2 Ni(dppe)} 2的固态结构揭示了两个镍离子占据独特的配位环境：一个镍处于方形平面S 2 P 2配位环境（τ 4 = 0.19），具有3.45 Å的Ni···V长距离；另一个镍处于四面体 S 2 P 2配位环境 (τ 4= 0.84) 和 2.60 Å 的短 Ni-V
• Synthesis and Characterization of a Redox-Active Bis(thiophenolato)amide Ligand, [SNS]^3–, and the Homoleptic Tungsten Complexes, W[SNS]₂ and W[ONO]₂
  作者：David W. Shaffer、Géza Szigethy、Joseph W. Ziller、Alan F. Heyduk

  DOI：10.1021/ic302506e

  日期：2013.2.18

  A new tridentate redox-active ligand platform, derived from bis(2-mercapto-p-toly)amine, [SNScat]H-3, has been prepared in high yields by a four-step procedure starting from commericially available bis(p-tolyl)amine. The redox-active pincer-type ligand has been coordinated to tungsten to afford the six-coordinate, homoleptic complex W[SNS](2). To benchmark the redox behavior of the [SNS] ligand, the analogous tungsten complex of the well-known redox-active bis(3,5-di-tert-butylphenolato)amide ligand, W[ONO](2), also has been prepared. Both complexes show two reversible reductions and two partially reversible oxidations. Structural, spectroscopic, and electrochemical data all indicate that W[ONO](2) is best described as a tungsten(VI) metal center coordinated to two [ONOcat](3-) ligands. In contrast, experimental data suggests a higher degree of S -> W pi donation, giving the W[SNS](2) complex non-innocent electronic character that can be described as a tungsten(IV) metal center coordinated to two [SNSsq](2-) ligands.
• Hydrogen-Atom Noninnocence of a Tridentate [SNS] Pincer Ligand
  作者：Kyle E. Rosenkoetter、Michael K. Wojnar、Bronte J. Charette、Joseph W. Ziller、Alan F. Heyduk

  DOI：10.1021/acs.inorgchem.8b00618

  日期：2018.8.20

  Double deprotonation of bis(2-mercapto-4-methylphenyl)amine ([SNS]H-3) followed by addition to NiCl2(PR3)(2) in air-free conditions afforded [SN(H)S]Ni(PR3) (1a, R = Cy; 1b, R = Ph) complexes, characterized as diamagnetic, square-planar nickel(II) complexes. When the same reaction was conducted with 3 equiv of KH, the diamagnetic anions K[SNS]Ni(PR3)} were obtained (K[2a], R = Cy; K[2b], R = Ph). In the presence of air, the reaction proceeds with a concomitant one-electron oxidation. When R = Cy, a square-planar, S = 1/2 complex, [SNS]Ni(PCy3) (3a), was isolated. When R = Ph, the bimetallic complex [SNS]Ni(PPh3)}(2) (3b}(2)) was obtained. This bimetallic species is diamagnetic; however, in solution it dissociates to give S = 1/2 monomers analogous to 3a. Complexes 1-3 represent a hydrogen-atom-transfer series. The bond dissociation free energies (BDFEs) for 1a and 1b were calculated to be 63.9 +/- 0.1 and 62.4 +/- 0.2 kcal mol(-1), respectively, using the corresponding pK(a) and E degrees' values. Consistent with these BDFE values, TEMPO center dot reacted with la and 1b, resulting in the abstraction of a hydrogen atom to afford 3a and 3b, respectively.