N,N'-dibenzyl-1H-pyrrole-2,5-dicarbothioamide | 905559-61-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: N,N'-dibenzyl-1H-pyrrole-2,5-dicarbothioamide
• 英文别名: N,N'-dibenzyl-2,5-1H-pyrroledicarbothioamide；2-N,5-N-dibenzyl-1H-pyrrole-2,5-dicarbothioamide
• CAS: 905559-61-7
• 化学式: C₂₀H₁₉N₃S₂
• 分子量: 365.523
• InChiKey: YVGFIYYSBDYNSR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  25
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  104
• 氢给体数：
  3
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N,N'-dibenzyl-1H-pyrrole-2,5-dicarbothioamide 、 potassium tetrachloropalladate(II) 以 not given 为溶剂， 以98%的产率得到[PdCl(κ(3)-SNS-N,N'-dibenzyl-1H-pyrrole-2,5-dicarbothioamide-1H)]
  参考文献：
  名称：

  Synthesis and Structural Features of a Series of κ³SNS Pincer Complexes of Group 10 Metals σ-Bonded to Centered Pyrrolate Unit

  摘要：

  N,N′-二苄基-1H-吡咯-2,5-二硫代甲酰胺的 N-金属化作用产生了具有 κ3SNS 型配位的第 10 族金属的新钳形配合物。这些配合物的分子结构通过 X 射线晶体学进行了表征。

  DOI：

  10.1246/cl.2006.558
• 作为产物：
  描述：

  1H-吡咯-2,5-二甲醛 、 苄胺 在 sulfur 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 5.0h， 以80%的产率得到N,N'-dibenzyl-1H-pyrrole-2,5-dicarbothioamide
  参考文献：
  名称：

  Synthesis and Structural Features of a Series of κ³SNS Pincer Complexes of Group 10 Metals σ-Bonded to Centered Pyrrolate Unit

  摘要：

  N,N′-二苄基-1H-吡咯-2,5-二硫代甲酰胺的 N-金属化作用产生了具有 κ3SNS 型配位的第 10 族金属的新钳形配合物。这些配合物的分子结构通过 X 射线晶体学进行了表征。

  DOI：

  10.1246/cl.2006.558

文献信息

• Deprotonation/protonation of coordinated secondary thioamide units of pincer ruthenium complexes: Modulation of voltammetric and spectroscopic characterization of the pincer complexes
  作者：Takuya Teratani、Take-aki Koizumi、Takakazu Yamamoto、Koji Tanaka、Takaki Kanbara

  DOI：10.1039/c0dt01283a

  日期：——

  New pincer ruthenium complexes, [Ru(SCS)(tpy)]PF6 (1) (SCS = 2,6-bis(benzylaminothiocarbonyl)phenyl), tpy = 2,2′:6′,2′'-terpyridyl) and [Ru(SNS)(tpy)]PF6 (2) (SNS = 2,5-bis(benzylaminothiocarbonyl)pyrrolyl), having κ3SCS and κ3SNS pincer ligands with two secondary thioamide units were synthesized by the reactions of [RuCl3(tpy)] with N,N'-dibenzyl-1,3-benzenedicarbothioamide (L1) and N,N'-dibenzyl-2,5-1H-pyrroledicarbothioamide (L2), respectively, and their chemical and electrochemical properties were elucidated. The structure of 1 was determined by X-ray crystallography. The complexes 1 and 2 showed a two-step deprotonation reaction by treatment with 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU), and the addition of DBU led to a shift of the metal-centered redox couples to a lower potential by 720 and 550 mV, respectively. The di-deprotonated complexes were also studied by 1H-NMR and UV-vis spectroscopy. The addition of methanesulfonic acid (MSA) to the di-deprotonated complexes enabled the recovery of 1 and 2, indicating that the thioamide moiety underwent a reversible deprotonation-protonation process, which resulted in regulating the redox potentials of the metal center. The Pourbaix diagram of 1 revealed that 1 underwent a one-proton/one-electron transfer process in the pH range of 5.83–10.35, and a two-proton/one-electron process at a pH of over 10.35, indicating that the deprotonation/protonation process of the complexes is related to proton-coupled electron transfer (PCET).

  新的钳形钌配合物[Ru(SCS)(tyy)]PF6 (1)（SCS = 2,6-双(苄氨基硫代羰基)苯基，tyy = 2,2′：通过[RuCl3(typy)]与 N、N'-二苄基-1,3-苯二硫代甲酰胺（L1）和 N,N'-二苄基-2,5-1H-吡咯烷二硫代甲酰胺（L2）反应合成了[RuCl3(tpy)]，并阐明了它们的化学和电化学性质。通过 X 射线晶体学确定了 1 的结构。配合物 1 和 2 经 1,8-二氮杂双环[5,4,0]十一-7-烯（DBU）处理后发生了两步去质子化反应，DBU 的加入导致以金属为中心的氧化还原偶分别向低电位移动了 720 mV 和 550 mV。二去质子化配合物还通过 1H-NMR 和 UV-vis 光谱进行了研究。在二去质子化的配合物中加入甲磺酸（MSA）后，1 和 2 得以恢复，这表明硫酰胺分子经历了可逆的去质子化-质子化过程，从而调节了金属中心的氧化还原电位。1 的 Pourbaix 图显示，1 在 pH 值为 5.83-10.35 的范围内经历了一个质子/一个电子转移过程，而在 pH 值超过 10.35 时则经历了一个双质子/一个电子转移过程，这表明配合物的去质子化/质子化过程与质子耦合电子转移（PCET）有关。
• Versatile bridging ability of secondary thioamide group for constructing metal cluster based on pincer complex
  作者：Ken Okamoto、Junpei Kuwabara、Takaki Kanbara

  DOI：10.1016/j.jorganchem.2010.11.028

  日期：2011.3

  The crystallization of the SCS pincer platinum complex with secondary thioamide groups, [4-methyl-2,6-bis(anilinothiocarbonyl)-kappa S-2,S'-phenyl-kappa C-1]chloroplatinum(II), spontaneously forms a trinuclear cluster complex accompanied by liberating HCl in DMSO/EtOH mixture. The crystal structure of the SNS pincer copper complex with secondary thioamide groups, [2,5-bis(benzylaminothiocarbonyl)-kappa S-2,S'-pyrrolyl-kappa N-1] chlorocopper(II), exhibits a dimer structure bearing the bridging thioamide group. The thioamide group acts as the bridging ligand of the multimetallic complexes in different anionic and neutral manners. (C) 2010 Elsevier B. V. All rights reserved.
• Nickel(II) complexes bearing a pincer ligand containing thioamide units: Comparison between SNS- and SCS-pincer ligands
  作者：Take-aki Koizumi、Takuya Teratani、Ken Okamoto、Takakazu Yamamoto、Yukihiro Shimoi、Takaki Kanbara

  DOI：10.1016/j.ica.2010.04.012

  日期：2010.8

  Nickel(II) complexes bearing a kappa(3)SNS pincer ligand, 2,5-bis(benzylaminothiocarbonyl)pyrrolyl (L1) and a kappa(3)SCS-pincer ligand, 2,6-bis(benzylaminothiocarbonyl)phenyl (L2), were synthesized, and their structures and electrochemical properties were elucidated. The crystal structures of [Ni(SNS)Br] (2) and [Ni(SCS)Br] (5) were determined by X-ray crystallography. The electrochemical and crystallographic data obtained from the complexes revealed that the kappa(3)SCS ligand has a stronger electron-donating ability than the kappa(3)SNS ligand. (C) 2010 Elsevier B.V. All rights reserved.