pyrido[2,3-b]pyrazine-2,3-dithiol | 114391-49-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氮杂萘
• 英文名称: pyrido[2,3-b]pyrazine-2,3-dithiol
• 英文别名: H2ppdt；1,4-dihydropyrido[2,3-b]pyrazine-2,3-dithione
• CAS: 114391-49-0
• 化学式: C₇H₅N₃S₂
• 分子量: 195.269
• InChiKey: KKMCMNVRVFBLHJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  12
• 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：
  101
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  nickel(II) chloride hexahydrate 、 pyrido[2,3-b]pyrazine-2,3-dithiol 在 sodium hydroxide 作用下， 以 甲醇 为溶剂， 反应 0.5h， 以81%的产率得到C₁₄H₆N₆NiS₄^(2-)*6H₂O*2Na⁽¹⁺⁾
  参考文献：
  名称：

  使用配体为中心的质子耦合电子转移路径提供可调节的超电势的分子镍氢放出催化剂系列

  摘要：

  已对两种新的二硫代镍镍衍生物对氢释放反应（HER）的电催化活性进行了研究，试图阐明是否可以通过改变以催化剂为中心触发以HER为中心的配体中心还原电位来调节HER的超电势。我们证明了这种方法在HER的过电位中实现理想的可调性的有效性。

  DOI：

  10.1039/c8cc07467d

文献信息

• Synthesis, structural characterization and electrochemical studies of [Fe2(μ-L)(CO)6] and [Fe2(μ-L)(CO)5(PPh3)] (L = pyrazine-2,3-dithiolate, quinoxaline-2,3-dithiolate and pyrido[2,3-b]pyrazine-2,3-dithiolate): Towards modeling the active site of [FeFe]–Hydrogenase
  作者：Gummadi Durgaprasad、Ramababu Bolligarla、Samar K. Das

  DOI：10.1016/j.jorganchem.2011.06.007

  日期：2011.9

  The reaction of heterocyclic 1,2-ene-dithiol ligands, namely, pyrazine-2,3-dithiol (H(2)pydt), quinoxaline-2,3-dithiol (H(2)qdt) and pyrido[2,3-b]pyrazine-2,3-dithiol (H(2)ppdt) with Fe-2(CO)(9) yields the '[FeFe]-hydrogenase' model complexes [Fe-2mu-pydt}(CO)(6)] (1), [Fe-2mu-qdt}(CO)(6)] (2) and [Fe-2mu-ppdt}(CO)(6)] (3), respectively. A further reaction of complexes 1, 2 and 3 with PPh3 in the presence of equimolar amount of decarbonylating agent Me3NO in CH3CN at room temperature resulted in the formation of unsymmetrical mono-PPh3-substituted model complexes [Fe-2mu-pydt}(CO)(5)PPh3] (4), [Fe-2mu-qdt}(CO)(5)PPh3] (5) and [Fe-2mu-ppdt}(CO)(5)PPh3] (6), respectively. The complexes 1-6 were well characterized by routine elemental analysis, IR, H-1 NMR, C-13 NMR spectroscopy and unambiguously characterized by X-ray crystallographic analysis. IR spectroscopy and electrochemical analysis show that an increase of the electron-withdrawing character of the bridging ligands (where electron-withdrawing character is in the order of pydt(2-) > ppdt(2-) >= qdt(2-)) leads to a decreased electron density at the iron centers, which yield a milder reduction potential and higher CO stretching frequencies. All the compounds 1-6 are further characterized by electrochemical studies. (C) 2011 Elsevier B.V. All rights reserved.
• PAPAVASSILIOU, G. C.;YIANNOPOULOS, S. Y.;ZAMBOUNIS, J. S., CHEM. SCR., 27,(1987) N 2, 265-268
  作者：PAPAVASSILIOU, G. C.、YIANNOPOULOS, S. Y.、ZAMBOUNIS, J. S.

  DOI：——

  日期：——
• A nitrogen rich Ni(II)–dithiolate system exhibiting acid–base behavior: Synthesis, supramolecular structure and spectroscopy of [Bu4N]2[NiII(ppdt)2] (ppdt=pyrido[2,3-b]pyrazine-2,3-dithiolate)
  作者：Ramababu Bolligarla、Gummadi Durgaprasad、Samar K. Das

  DOI：10.1016/j.inoche.2009.02.008

  日期：2009.5

  The compound [Bu4N](2)[Ni(ppdt)(2)] (1) (ppdt = pyrido[2,3-b]pyrazine-2,3-dithiolate) has been synthesized, starting from pyrido[2,3-bipyrazine-2,3-dithiol, nickel chloride and tetrabutylammonium bromide in methanol. Compound 1 crystallizes in P2(1)/c space group (monoclinic system). Its crystal structure is characterized by interesting C-H center dot center dot center dot S and C-H center dot center dot center dot N supramolecular weak interactions. Its solution state has been described with acid-base (protonation-deprotonation) behavior, that has rarely been investigated for a metal-dithiolene system. Compound 1 is first instance of a metal-dithiolene compound that has three ring nitrogen on each dithiolate ligand. The pH dependent changes in the charge-transfer absorption band are attributed to the protonation on an imine nitrogen of the ppdt ligand. The complex is electrochemically quasi-reversible with an oxidation potential of E-1/2 = +0.46V vs. Ag/AgCl in methanol. (c) 2009 Elsevier B.V. All rights reserved.
• Acid–base behavior of a simple metal bis(dithiolate) system: Synthesis, crystal structure and spectroscopy of [Bu4N]2[MII(ppdt)2] (M=Ni, Pt; ppdt=pyrido[2,3-b]pyrazine-2,3-dithiolate)
  作者：Ramababu Bolligarla、Ravada Kishore、Gummadi Durgaprasad、Samar K. Das

  DOI：10.1016/j.ica.2010.03.060

  日期：2010.10

  The syntheses, crystal structures and properties of compounds [Bu4N](2)[Ni(ppdt)(2)] (1) and [Bu4N](2)[Pt(ppdt)(2)] (2) (ppdt = pyrido[2,3-b] pyrazine-2,3-dithiolate) have been described. Compound 1 crystallizes in P2(1)/c space group (monoclinic system), whereas compound 2 crystallizes in C2/c space group (monoclinic system). The crystal structures of both compounds 1 and 2 have been characterized by C-H center dot center dot center dot S and C-H center dot center dot center dot N hydrogen bonding interactions between cation and anions resulting in threedimensional supramolecular networks in the crystals of 1 and 2, respectively. The acid-base behavior of the ground states of both [Bu4N](2)[Ni(ppdt)(2)] (1) and [Bu4N](2)[Pt(ppdt)(2)] (2) and also the excited state of compound [Bu4N](2)[Pt(ppdt)(2)] (2) in solutions has been studied. The pH dependent changes in the charge transfer absorption and emission spectra are attributed to the protonation on an imine nitrogen of the ppdt ligand. The ground-state basicity constants of the two complexes 1 and 2 have been determined from spectrophotometric analysis by titrating with an weak acid, yielding pK(b1) = 8.0 for complex [Bu4N](2)[Ni(ppdt)(2)] (1) and pK(b1) = 7.8 for complex [Bu4N](2)[Pt(ppdt)(2)] (2). The excited-state basicity constant pK(b1)*for complex [Bu4N](2)[Pt(ppdt)(2)] (2) has been determined by a thermodynamic equation using a Frster analysis yielding the value of 1.8. The complex 2 is electrochemically irreversible with an oxidation potential of E-1/2 = + 0.41 V versus Ag/AgCl in methanol. (C) 2010 Elsevier B. V. All rights reserved.