[1,3]diselenole-2-thione | 53555-46-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: [1,3]diselenole-2-thione
• 英文别名: 1,3-diselenole-2-thione；1,3-Diselenol-2-thion
• CAS: 53555-46-7
• 化学式: C₃H₂SSe₂
• 分子量: 228.035
• InChiKey: LPADEYIEYQACFQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.53
• 重原子数：
  6
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  32.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  [1,3]diselenole-2-thione 在 lithium diisopropyl amide 、 一氯化碘 作用下， 生成 4,5-diiodo[1,3]thiaselenole-2-selone
  参考文献：
  名称：

  [1,3]二硒烯-2-硫酮的无CSe2合成及其在碘化四硒富勒烯（TSeFs）合成中的应用。

  摘要：

  我们开发了一种新的不含CSe2的方案，用于合成[1,3]二硒烯-2-硫酮，并将其转化为四硒富勒烯衍生物，而没有任何硒-硫交换副反应。

  DOI：

  10.1039/b304136k
• 作为产物：
  描述：

  (4-Carboxy-[1,3]diselenol-2-ylidene)-methyl-sulfonium; iodide 在 吡啶 作用下， 以 苯 为溶剂， 反应 14.0h， 以76%的产率得到[1,3]diselenole-2-thione
  参考文献：
  名称：

  [1,3]二硒烯-2-硫酮的无CSe2合成及其在碘化四硒富勒烯（TSeFs）合成中的应用。

  摘要：

  我们开发了一种新的不含CSe2的方案，用于合成[1,3]二硒烯-2-硫酮，并将其转化为四硒富勒烯衍生物，而没有任何硒-硫交换副反应。

  DOI：

  10.1039/b304136k

文献信息

• Synthesis of novel selenium-containing donors as selenium analogues of diiodo(ethylenedithio)diselenadithiafulvalene (DIETS)Electronic supplementary information (ESI) available: Experimental details. See http://www.rsc.org/suppdata/ob/b4/b406092j/
  作者：Takashi Shirahata、Tatsuro Imakubo

  DOI：10.1039/b406092j

  日期：——

  Novel selenium analogues of diiodo(ethylenedithio)diselenadithiafulvalene (DIETS) have been successfully derived from 1,3-diselenole-2-thione, which could be synthesized without the use of the highly toxic reagent CSe2.

  新型硒类似物二碘(乙撑二硫)二硒二硫富瓦烯 (DIETS) 已成功从 1,3-二硒醇-2-硫酮衍生而来，无需使用剧毒试剂 CSe2 即可合成。
• Hybrid Organic/Inorganic Supramolecular Conductors D ₂ [Au(CN) ₄ ] [D = Diiodo(ethylenedichalcogeno)tetrachalcogenofulvalene], Including a New Ambient Pressure Superconductor
  作者：Tatsuro Imakubo、Takashi Shirahata、Megumi Kibune、Hiroko Yoshino

  DOI：10.1002/ejic.200700530

  日期：2007.10

  highly toxic reagent CSe2, and their Au(CN)4 salts have been prepared by electrochemical oxidation. Characteristic I···N iodine bonds are constructed in all crystals, and their packing motifs are classified into two groups by the difference in the space group symmetry. The salt of DIEDSS crystallizes in the monoclinic C2/c space group and a novel helical supramolecular architecture is constructed by the

  五种二碘（亚乙基二硫属）四硫属元素富瓦烯，DIEDSS 2-(5,6-dihydro[1,3]diselenolo[4,5-b][1,4]diselenin-2-ylidene)-4,5-diiodo-1， 3-二硫醇}, DIET-STF 2-(4,5-diiodo-1,3-diselenol-2-ylidene)-5,6-dihydro[1,3]dithiolo[4,5-b][1, 4]dithiine}, DIEDS-STF 2-(4,5-diiodo-1,3-diselenol-2-ylidene)-5,6-dihydro[1,4]diselenino[2,3-d][1, 3]dithiole}, DIETSe 2-(4,5-diiodo-1,3-diselenol-2-ylidene)-5,6-dihydro[1,3]diselenolo[4,5-b][1,4] dithiine}
• New organic conductors based on dibromo- and diiodo-TSeFs with magnetic and non-magnetic MX4 counter anions (M = Fe, Ga; X = Cl, Br)
  作者：Takashi Shirahata、Megumi Kibune、Mitsuhiko Maesato、Tomohito Kawashima、Gunzi Saito、Tatsuro Imakubo

  DOI：10.1039/b605420j

  日期：——

  Eight cation radical salts based on halogenated tetraselenafulvalene (TSeF) derivatives, dibromo(ethylenedithio)tetraselenafulvalene (DBrETSe) and diiodo(ethylenedithio)tetraselenafulvalene (DIETSe), were prepared using magnetic and non-magnetic MX4 counter anions (M = Fe, Ga; X = Cl, Br). Crystal structures of the DBrETSe salts depend on the halogen species on the MX4 counter anion. The MCl4 salts of DBrETSe are isostructural and crystallize in the orthorhombic space group Ibam and those of the MBr4 salts crystallize in the monoclinic space group C2/c. On the other hand, all four MX4 salts of DIETSe are isostructural and crystallize in the orthorhombic space group Ibam. In all eight crystals, donor molecules form a so-called β-type molecular arrangement and characteristic halogen bonds between the halogen atoms on the edge of the donor molecules and those of the counter anions are observed. (DBrETSe)2MX4 (M = Fe, Ga; X = Cl, Br) show stable metallic behaviour down to 4.2 K. This is in contrast to their iodinated analogues (DIETSe)2MCl4 (M = Fe, Ga), which show a metal–semiconductor transition at 11 K for the FeCl4 salt and at 12 K for the GaCl4 salt. No metal–semiconductor transition is observed for (DIETSe)2GaBr4, which contains the non-magnetic anion, but the transition is observed at 7.2 K for the corresponding FeBr4 salt, which contains a magnetic anion, indicating that the metal–semiconductor transition of (DIETSe)2FeBr4 correlates to the π–d electronic interaction through the I⋯Br halogen bonds. Antiferromagnetic orderings of d spins of the FeX4 anions are observed in (DBrETSe)2FeX4 and (DIETSe)2FeX4 (X = Cl, Br). In contrast to the low Néel temperature (TN ≈ 2.5 K) of the FeCl4 salts, the antiferromagnetic orderings occur at relatively high temperatures, i.e.TN = 7.5 K for (DBrETSe)2FeBr4 and TN = 7.0 K for (DIETSe)2FeBr4. Since the metallic state of (DBrETSe)2FeBr4 remains below TN, this salt is classified as a novel antiferromagnetic organic metal. On the other hand, the antiferromagnetic ordering of the d spins in (DIETSe)2FeBr4 takes place cooperatively with the metal–semiconductor transition around 7 K. These antiferromagnetic orderings of the d spins between the FeX4 anions cannot be explained by direct anion–anion interactions because of their long halogen⋯halogen distances between the FeX4 anions, and the importance of the π–d interaction between the donors and the counter anions through the halogen bonds is strongly suggested.

  利用磁性和非磁性 MX4 反阴离子（M = Fe、Ga；X = Cl、Br）制备了八种基于卤代四硒富戊烯（TSeF）衍生物、二溴（亚乙基二硫代）四硒富戊烯（DBrETSe）和二碘（亚乙基二硫代）四硒富戊烯（DIETSe）的阳离子自由基盐。DBrETSe 盐的晶体结构取决于 MX4 反阴离子上的卤素种类。DBrETSe 的 MCl4 盐具有等长结构，在正交空间群 Ibam 中结晶，而 MBr4 盐则在单斜空间群 C2/c 中结晶。另一方面，DIETSe 的所有四种 MX4 盐都是等结构的，并在正交空间群 Ibam 中结晶。在所有八种晶体中，供体分子形成了所谓的 β 型分子排列，供体分子边缘的卤素原子与反阴离子的卤素原子之间形成了特征性的卤素键。(DBrETSe)2MX4（M = Fe、Ga；X = Cl、Br）在低至 4.2 K 的温度下表现出稳定的金属特性。这与它们的碘化类似物 (DIETSe)2MCl4（M = Fe、Ga）形成了鲜明对比，后者在 11 K 时（FeCl4 盐）和 12 K 时（GaCl4 盐）出现了金属-半导体转变。含有非磁性阴离子的 (DIETSe)2GaBr4 没有观察到金属-半导体转变，但含有磁性阴离子的相应 FeBr4 盐在 7.2 K 时观察到了转变，这表明 (DIETSe)2FeBr4 的金属-半导体转变与通过 I⋯Br 卤素键的π-d 电子相互作用有关。在 (DBrETSe)2FeX4 和 (DIETSe)2FeX4 (X = Cl, Br) 中观察到了 FeX4 阴离子 d 自旋的反铁磁有序性。与 FeCl4 盐的低奈尔温度（TN ≈ 2.5 K）相反，反铁磁有序出现在相对较高的温度下，即 (DBrETSe)2FeBr4 的 TN = 7.5 K 和 (DIETSe)2FeBr4 的 TN = 7.0 K。由于 (DBrETSe)2FeBr4 的金属态保持在 TN 以下，因此这种盐被归类为新型反铁磁性有机金属。另一方面，(DIETSe)2FeBr4 中 d 自旋的反铁磁排序与 7 K 附近的金属-半导体转变协同发生。由于 FeX4 阴离子之间的卤素⋯卤素距离较长，阴离子-阴离子之间的直接相互作用无法解释这些 d 自旋的反铁磁排序。
• Neue selenreiche 1,3-Dichalkogenol-2-selone via 4,5-Dilithio-1,3-dichalkogenol-2-selone
  作者：Helmut Poleschner、Reiner Radeglia、Joachim Fuchs

  DOI：10.1016/0022-328x(92)83086-w

  日期：1992.4

  1,3-Dithiole-2-thione (1), 1,3-diselenole-2-selone (2), 1,3-thiaselenole-2-thione (3), 1,3-dithiole-2-selone (4), 1,3-diselenole-2-thione (5) and 1,3-thiaselenole-2-selone (6) are dilithiated with lithium diisopropyl amide in the 4/5 position, followed by selenation (thiolation) and complexation of the resulting heterocyclic diselenolates (dithiolates) to the zinc bis-chelates (tetrabutylammonium or tetraphenylphosphonium salts).These zinc complexes react with benzoyl chloride to the corresponding selenole and thiole esters. It is noteworthy that the heterocyclic thiones with one or two ring selenium atoms undergo ring transformation (Dimroth rearrangement) during the lithiation chalcogenation sequence, whilst the thione sulfur and one ring selenium atom change their places: 3 --> 1,3-dithiole-2-selone-4,5-diselenolate or dithiolate structure, 5 --> 1,3-thiaselenole-2-selone-4,5-diselenolate structure. This observed rearrangement is verified by independent synthetic pathways. The corresponding identical zinc chelates 12 and complex 18 result from the precursors 3 and 4, and 5 and 6, respectively. Trapping experiments support the conclusion that this rearrangement takes place already during lithiation. The zinc chelates and thiole and selenole esters are characterized in detail by IR and above all by C-13 and Se-77 NMR spectroscopy, including NMR shift values of the precursor heterocycles. The X-ray crystal structure determination of bis(tetraphenylphosphonium)-bis(1,3-thiaselenole-2-selone-4,5-diselenolato) zincate (18), obtained from 5, shows the rearrangement of 5 to the 1,3-thiaselenole-2-selone partial structure in 18.
• Poleschner, H.; Fanghaenel, E., Journal fur praktische Chemie (Leipzig 1954), 1982, vol. 324, # 4, p. 691 - 696
  作者：Poleschner, H.、Fanghaenel, E.

  DOI：——

  日期：——