4,5-bis(2'-cyanoethylseleno)-N-methyl-1,3-thiazoline-2-thione | 1000978-69-7

• 分子结构分类: 有机化合物
• 英文名称: 4,5-bis(2'-cyanoethylseleno)-N-methyl-1,3-thiazoline-2-thione
• 英文别名: N-methyl-bis(cyanoethylseleno)-1,3-thiazoline-2-thione；4,5-bis(2'-cyanoethylseleno)-1,3-thiazol-2-thione
• CAS: 1000978-69-7
• 化学式: C₁₀H₁₁N₃S₂Se₂
• 分子量: 395.269
• InChiKey: XYVZSCOBRQHAKD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.14
• 重原子数：
  17.0
• 可旋转键数：
  6.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  52.51
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  二氯二茂钛 、 4,5-bis(2'-cyanoethylseleno)-N-methyl-1,3-thiazoline-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-diselenolato)]
  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 、 selenium 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以43%的产率得到4,5-bis(2'-cyanoethylseleno)-N-methyl-1,3-thiazoline-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

• Mixed-valence gold bis(diselenolene) complex turning metallic under pressure
  作者：Yann Le Gal、HengBo Cui、Pere Alemany、Enric Canadell、Reizo Kato、Thierry Roisnel、Vincent Dorcet、Marc Fourmigué、Dominique Lorcy

  DOI：10.1039/d1tc02751d

  日期：——

  complex in the conducting layers. The salt is semiconducting (σRT = 3 × 10−2 S cm−1, Eact = 0.137 eV) but, in contrast with other 1 : 2 gold bis(dithiolene) salts, turns metallic under pressure (>10 GPa). [Ph4P][Au(Me-thiazds)2]2 is thus the first metallic, fully characterized, 1 : 2 mixed-valence gold complex, opening the door for the preparation of highly conducting solids of this type.

  虽然 d 8阴离子金双（二硫烯）配合物的氧化最常提供相应的中性自由基单组分导体，但作为 Ph 4 P +盐分离的原始金双（二硫烯）配合物在电结晶时提供混合价 1 : 2盐，[Ph 4 P][Au(Me-thiazds) 2 ] 2 (Me-thiazds: 2-methyl-1,3-thiazoline-2-thione-4,5-diselenolate)。这种盐表现出罕见的电荷交替，与导电层中金络合物的顺式和反式异构体同时存在有关。盐是半导体的 ( σ RT = 3 × 10 -2 S cm-1 , E act = 0.137 eV) 但是，与其他 1 : 2 金双（二硫烯）盐相比，在压力（> 10 GPa）下变成金属。[Ph 4 P][Au(Me-thiazds) 2 ] 2因此是第一种完全表征的金属1:2混合价金配合物，为制备此类高导电固体打开了大门。
• 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
• On the Role of Chalcogen Donor Atoms in Diimine‐Dichalcogenolate Pt ^II SONLO Chromophores: Is It Worth Replacing Sulfur with Selenium?
  作者：Anna Pintus、M. Carla Aragoni、Francesco Isaia、Vito Lippolis、Dominique Lorcy、Alexandra M. Z. Slawin、J. Derek Woollins、Massimiliano Arca

  DOI：10.1002/ejic.201500777

  日期：2015.11

  Two new diimine-diselenolate Pt-II chromophores [Pt(bipy)(Me-dset)] (1) and [Pt(phen)(Me-dset)] (2) (Me-dset(2-) = N-methyl-2-thioxothiazoline-4,5-diselenolate) were synthesized and characterized. The effect of replacing sulfur with selenium was investigated by comparing the UV/Vis spectroscopic and electrochemical properties of 1 and 2 with those of the corresponding sulfur analogues, [Pt(bipy)(Me-dmet)]

  两个新的二亚胺二硒化 Pt-II 发色团 [Pt(bipy)(Me-dset)] (1) 和 [Pt(phen)(Me-dset)] (2) (Me-dset(2-) = N-methyl -2-thioxothiazoline-4,5-diselenolate) 合成并表征。通过比较 1 和 2 的紫外/可见光谱和电化学性质与相应的硫类似物 [Pt(bipy)(Me-dmet)] (3) 和 [Pt(phen) )(Me-dmet)] (4)，特别关注它们的线性和非线性光学特性
• Mixed-Valence Conductors from Ni Bis(diselenolene) Complexes with a Thiazoline Backbone
  作者：Hadi Hachem、HengBo Cui、Reizo Kato、Pere Alemany、Enric Canadell、Olivier Jeannin、Marc Fourmigué、Dominique Lorcy

  DOI：10.1021/acs.inorgchem.2c04300

  日期：2023.3.13

  multi-component nickel bis(diselenolene) salts were obtained by electrocrystallization of the monoanionic species [Ni(Me-thiazds)2]−1 (Me-thiazds: N-methyl-1,3-thiazoline-2-thione-4,5-diselenolate), with 1:2 and 1:3 stoichiometries depending of the counter ion used (Et4N+ and nBu4N+vs Ph4P+, respectively). This behavior strongly differs from that of the corresponding monoanionic dithiolene complexes whose oxidation

  通过单阴离子物种 [Ni(Me-thiazds) 2 ] -1 ( Me -thiazds: N -methyl-1,3-thiazoline- 2-thione-4,5-diselenolate)，化学计量比为 1:2 和 1:3，具体取决于所用的抗衡离子（分别为 Et 4 N +和n Bu 4 N +与Ph 4 P +）。这种行为与相应的单阴离子二硫杂环丁烯的行为截然不同其氧化提供单组分中性物质的配合物。这提供了镍二硒烯络合物的混合价导电盐的其他罕见例子，仅在 dsit (1,3-dithiole-2-thione-4,5-diselenolate) 和 dsise (1,3-dithiole-) 的两个例子中已知2-selone-4,5-diselenolate) 配体。混合价盐形成高度二聚或三聚的双金属和三金属单元，这种镍配合物很少见。高压（高达 10 GPa）下的输运测量和能带结构计算证实了
• 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).