4,5-bis(2'-cyanoethylthio)-1,3-thiazol-2-thione | 1000978-68-6

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 4,5-bis(2'-cyanoethylthio)-1,3-thiazol-2-thione
• 英文别名: N-methyl-bis(cyanoethylthio)-1,3-thiazoline-2-thione；4,5-bis(2'-cyanoethylthio)-N-methyl-1,3-thiazoline-2-thione；N-methyl-4,5-bis(2-cyanoethylthio)-2-thioxothiazoline；3-[[5-(2-Cyanoethylsulfanyl)-3-methyl-2-sulfanylidene-1,3-thiazol-4-yl]sulfanyl]propanenitrile
• CAS: 1000978-68-6
• 化学式: C₁₀H₁₁N₃S₄
• 分子量: 301.481
• InChiKey: IZBLPHWPFZLXIB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  159
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  二氯二茂钛 、 4,5-bis(2'-cyanoethylthio)-1,3-thiazol-2-thione 在 cesium hydroxide monohydrate 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 以40%的产率得到[(cyclopentadienyl)2Ti(N-methyl-1,3-thiazoline-2-thione-4,5-dithiolato)]
  参考文献：
  名称：

  Titanocene complexes of the N-methyl and N-phenyl-1,3-thiazoline-2-thione-4,5-dithiolates and 4,5-diselenolate ligands

  摘要：

  Cp(2)Ti(dithiolene) and Cp(2)Ti(diselenolene) complexes containing the N-methyl-1,3-thiazoline-2-thione-4,5- dithiolate ligand (Me-thiazdt), the N-phenyl-1,3-thiazoline-2-thione-4,5-dithiolate ligand (Ph-thiazdt) and the N-methyl-1,3-thiazoline-2-thione-4,5-diselenolate ligand (Me-thiazds) have been synthesized. Three approaches have been developed in order to generate the dithiolene or the diselenolene ligands which were reacted with Cp(2)TiCl(2) to form the corresponding heteroleptic complexes. Their Xray crystal structures, UV-Vis absorption spectra as well as their redox properties, determined by cyclic voltammetry have been investigated and discussed. Variable-temperature (1)H NMR experiments have been performed in order to determine the activation energies of the chelate ring inversion. (c) 2008 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2008.05.021
• 作为产物：
  描述：

  3-溴丙腈 、 3-甲基-2(3H)-噻唑硫酮 在 lithium diisopropyl amide 、 1,2,3,4,5,6,7,8-八硫杂环辛烷 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以60%的产率得到4,5-bis(2'-cyanoethylthio)-1,3-thiazol-2-thione
  参考文献：
  名称：

  Titanocene complexes of the N-methyl and N-phenyl-1,3-thiazoline-2-thione-4,5-dithiolates and 4,5-diselenolate ligands

  摘要：

  Cp(2)Ti(dithiolene) and Cp(2)Ti(diselenolene) complexes containing the N-methyl-1,3-thiazoline-2-thione-4,5- dithiolate ligand (Me-thiazdt), the N-phenyl-1,3-thiazoline-2-thione-4,5-dithiolate ligand (Ph-thiazdt) and the N-methyl-1,3-thiazoline-2-thione-4,5-diselenolate ligand (Me-thiazds) have been synthesized. Three approaches have been developed in order to generate the dithiolene or the diselenolene ligands which were reacted with Cp(2)TiCl(2) to form the corresponding heteroleptic complexes. Their Xray crystal structures, UV-Vis absorption spectra as well as their redox properties, determined by cyclic voltammetry have been investigated and discussed. Variable-temperature (1)H NMR experiments have been performed in order to determine the activation energies of the chelate ring inversion. (c) 2008 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2008.05.021

文献信息

• Single-component conductors based on closed-shell Ni and Pt bis(dithiolene) complexes: metallization under high pressure
  作者：Hadi Hachem、HengBo Cui、Takao Tsumuraya、Reizo Kato、Olivier Jeannin、Marc Fourmigué、Dominique Lorcy

  DOI：10.1039/d0tc02868a

  日期：——

  Neutral, closed-shell nickel and platinum bis(dithiolene) complexes are explored as single-component conductors. Four complexes formulated as [Ni(R-thiazdt)2]0 and [Pt(R-thiazdt)2]0 (R-thiazdt: 2-alkyl-1,3-thiazoline-2-thione-4,5-dithiolate; R = Me, Et) were obtained by electrocrystallization from the corresponding monoanionic species. Crystal and electronic structures confirm their semi-conducting

  研究了中性的，闭壳的镍和铂双（二硫代双烯）络合物作为单组分导体。配制为[Ni（R-thiazdt）2 ] 0和[Pt（R-thiazdt）2 ] 0的四种配合物通过电结晶从相应的单阴离子物质中获得（R-噻唑特：2-烷基-1,3-噻唑啉-2-硫酮-4,5-二硫代酸酯； R = Me，Et）。晶体和电子结构证实了它们的半导体行为，并显示出乙基取代的（R = Et）配合物中存在较大的HOMO-LUMO间隙，而位阻较少的甲基取代的配合物则具有较高的电导率和较小的活化能。使用金刚石砧池（DAC）在镍系列中应用高质量的准静水压，可大大提高[Ni（Me-thiazdt）2 ] 0的电导率，最高可达166 S cm -1（E act = 0.1 meV ）在19 GPa。另一方面，N-乙基衍生物[Ni（Et-thiazdt）2 ] 0在压力达到4.4 GPa时在低温范围（<100 K）时变为金属，而将压力进一步提高到6
• Stable Metallic State of a Neutral-Radical Single-Component Conductor at Ambient Pressure
  作者：Yann Le Gal、Thierry Roisnel、Pascale Auban-Senzier、Nathalie Bellec、Jorge Íñiguez、Enric Canadell、Dominique Lorcy

  DOI：10.1021/jacs.8b03714

  日期：2018.6.6

  instances, with single-component systems. In that respect, gold bis(dithiolene) complexes, in their neutral radical state, provide a prototype platform toward such single-component conductors. Herein we report the first single-component molecular metal under ambient pressure derived from such Au complexes without any TTF backbone. This complex exhibits a conductivity of 750 S·cm-1 at 300 K up to 3800

  分子金属基本上是用基于四硫富瓦烯 (TTF) 的前体获得的，或者使用多组分离子材料，或者在少数情况下使用单组分系统。在这方面，金双（二硫烯）配合物在它们的中性自由基状态下，为这种单组分导体提供了一个原型平台。在这里，我们报告了在环境压力下从这种没有任何 TTF 主链的 Au 配合物衍生的第一种单组分分子金属。该配合物在 300 K 时的电导率为 750 S·cm-1，在 4 K 时高达 3800 S·cm-1。第一性原理电子结构计算表明，金属态的惊人稳定性源于相当大的内部电子转移从 SOMO-1 到复合体的 SOMO，以及大量的叠层间和层间相互作用。
• Variable Magnetic Interactions between S = 1/2 Cation Radical Salts of Functionalizable Electron-Rich Dithiolene and Diselenolene Cp₂Mo Complexes
  作者：Talia Bsaibess、Michel Guerro、Yann Le Gal、Daad Sarraf、Nathalie Bellec、Marc Fourmigué、Frédéric Barrière、Vincent Dorcet、Thierry Guizouarn、Thierry Roisnel、Dominique Lorcy

  DOI：10.1021/ic3025606

  日期：2013.2.18

  planar MoS2C2 (or MoSe2C2) metallacycles. All five complexes formed charge transfer salts with a weak (TCNQ) and a strong acceptor (TCNQF4), affording ten different charge-transfer salts, all with 1:1 stoichiometry. Crystal structure determinations show that the S/Se substitution in the metallacycle systematically affords isostructural salts, while the Cp2Mo(R-thiazdt) complexes with R equals ethyl or CH2CH2OH

  一系列含有N-烷基-1,3-噻唑啉-2-硫酮-4,5-二硫代酸酯配体的Cp 2 Mo（二硫代烯）和Cp 2 Mo（二硫代烯）配合物（R-噻唑，R = Me，Et，CH合成了2 CH 2 OH）和N-烷基-1,3-噻唑啉-2-硫酮-4,5-二硒酸酯配体（R-噻唑，R = Me，Et）。这些杂钼钼配合物已经通过电化学，光谱电化学和单晶X射线衍射表征。它们可作为非常好的电子供体配合物，其第一氧化电位比原型Cp 2 Mo（dmit）配合物低200 mV，并表现出几乎为平面的MoS 2 C 2（或MoSe 2 C 2））metallacycles。所有这五个络合物均形成具有弱受体（TCNQ）和强受体（TCNQF 4）的电荷转移盐，提供了十种不同的电荷转移盐，均具有1：1的化学计量比。晶体结构测定表明，金属环中的S / Se取代系统地提供了同构结构的盐，而具有R的Cp 2 Mo（R-thiazdt）络合物等于乙基或CH
• Influence of the Thiazole Backbone on the Structural, Redox, and Optical Properties of Dithiolene and Diselenolene Complexes
  作者：Samar Eid、Marc Fourmigué,、Thierry Roisnel、Dominique Lorcy

  DOI：10.1021/ic7013682

  日期：2007.12.1

  Metalation of N-methyl-1,3-thiazoline-2-thione followed by reaction with elemental S or Se affords a simple and efficient approach to N-methyl- 1,3-thiazoline-2-thione-4,5-dithiolate (Me-thiazdt) and the diselenolate (Me-thiazds) analogue. In the presence of metal II centers such as Zn, Ni, and Pd these ligands afford the corresponding dianionic dithiolene and diselenolene complexes. The Ni and Pd dianionic complexes are easily oxidized into the monoanionic species. Complexes were isolated and characterized by single-crystal X-ray crystallography. Most often a substitutional S/N-Me disorder is observed, attributable to the square-planar trans complexes disordered on two positions or coexistence of both cis and trans isomers on inversion centers. Monoanionic complexes exhibit a strong NIR absorption band with 6 values up to 33 750 M-1 cm(-1).
• Structure–Property Relationships in Pt ^II Diimine‐Dithiolate Nonlinear Optical Chromophores Based on Arylethylene‐1,2‐dithiolate and 2‐Thioxothiazoline‐4,5‐dithiolate
  作者：Anna Pintus、M. Carla Aragoni、Nathalie Bellec、Francesco A. Devillanova、Dominique Lorcy、Francesco Isaia、Vito Lippolis、Rebecca A. M. Randall、Thierry Roisnel、Alexandra M. Z. Slawin、J. Derek Woollins、Massimiliano Arca

  DOI：10.1002/ejic.201200346

  日期：2012.8

  AbstractEighteen new [PtII(N∧N)(S∧S)] complexes [23–40; N∧N = diimine: 2,2′‐bipyridine, 1,10‐phenanthroline and alkyl/aryl‐substituted derivatives; S∧S = arylethylene‐1,2‐dithiolate (R‐edt2–: R = phenyl, 2‐naphthyl, 1‐pyrenyl), N‐substituted 2‐thioxothiazoline‐4,5‐dithiolate (R‐dmet2–: R = methyl, ethyl, phenyl)] have been synthesized and characterized by spectroscopic (UV/Vis/NIR, fluorescence) and electrochemical (CV) measurements. Single‐crystal X‐ray diffraction analysis allowed structural characterization of five of the complexes (27–29, 31, and 37). Structural modifications capable of affecting the nature and energies of the frontier molecular orbitals in these systems were assessed and hybrid DFT and time‐dependent (TD) DFT calculations, carried out both in the gas phase and in the presence of several solvents (CH2Cl2, CHCl3, CH3CN, acetone, thf, dmf, dmso, and toluene), allowed the trends observed in the voltammetric data and in the energies of the peculiar solvatochromic visible absorption bands to be rationalized. In addition, to evaluate the second‐order nonlinear optical properties of 23–40, first static hyperpolarizability values βtot were calculated both in the gas phase and in CH2Cl2, the highest values being obtained for [Pt(N∧N)(Me‐dmet)] complexes (N∧N = 4,4′‐diphenyl‐2,2′‐bipyridine and 4,7‐diphenyl‐1,10‐phenanthroline; βtot = 691 × 10–30 and 604 × 10–30 esu, respectively).