4-cyano-5-trifluoromethyl-1,3-dithiole-2-one | 873932-54-8

• 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: 4-cyano-5-trifluoromethyl-1,3-dithiole-2-one
• 英文别名: 4-trifluoromethyl-5-cyano-2-oxo-1,3-dithiole；4-cyano-5-trifluoromethyl-1,3-dithiol-2-one；2-Oxo-5-(trifluoromethyl)-1,3-dithiole-4-carbonitrile
• CAS: 873932-54-8
• 化学式: C₅F₃NOS₂
• 分子量: 211.188
• InChiKey: DLUAZKPTYRYENY-UHFFFAOYSA-N

物化性质

• 沸点：
  210.5±50.0 °C(Predicted)
• 密度：
  1.74±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  91.5
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  ferrocenium(III) tetrafluoroborate 、 nickel(II) chloride hexahydrate 、 4-cyano-5-trifluoromethyl-1,3-dithiole-2-one 在 Na 、 MeOH 作用下， 以 甲醇 为溶剂， 以41%的产率得到[ferricinium][Ni(2-(trifluoromethyl)acrylonitrile-1,2-dithiolate)2] C8F6N2NiS4(1-)*C10H10Fe(1+), monoclinic
  参考文献：
  名称：

  Order−Disorder Transition Coupled with Magnetic Bistability in the Ferricinium Salt of a Radical Nickel Dithiolene Complex

  摘要：

  The ferricinium salt of the anionic, S = 1/2, dithiolene complex [Ni(tfadt)(2)](-) ( where tfadt is the asymmetrically substituted 2-(trifluoromethyl) acrylonitrile-1,2- dithiolate) crystallizes at room temperature (rt) into uniform chains of dithiolene complexes, separated by ferricinium cations. Both ionic entities are characterized by disorder affecting one CF3 and one Cp moiety. Above 250 K, this compound displays a Curie-type behavior. At lower temperatures, two first-order transitions around 249 and 137 K are revealed by susceptibility measurements and the observation of hysteresis effects. Crystal structure determinations performed at 230 and 120 K show that the high-temperature transition is associated with an ordering of the CF3 and Cp groups together with a dimerization of the anionic stacks that thus induces a drop of the susceptibility. The second, low-temperature transition leads to a tetramerization of these nickel dithiolene stacks now in a complete diamagnetic state while the remaining susceptibility originates from the sole ferricinium contribution. The first order character of the 249 K transition with its associated bistable behavior is likely correlated with the structural order-disorder transition, an original behavior in this class of materials where bistability is most often associated with a strengthening of interstack intermolecular interactions ( hydrogen bonding, pi-pi interactions...).

  DOI：

  10.1021/ja064842v

文献信息

• Between Ni(mnt)₂ and Ni(tfd)₂ Dithiolene Complexes:  the Unsymmetrical 2-(Trifluoromethyl)acrylonitrile-1,2-dithiolate and Its Nickel Complexes
  作者：Olivier Jeannin、Jacques Delaunay、Frédéric Barrière、Marc Fourmigué

  DOI：10.1021/ic051226b

  日期：2005.12.1

  dianionic diamagnetic [Ni(tfadt)(2)](2)(-) and their monoanionic paramagnetic [Ni(tfadt)(2)](*)(-) forms, are reported, as n-Bu(4)N(+), PPh(4)(+), and (18-crown-6)Na(+) salts, respectively. In the [(18-crown-6)Na](2)[Ni(tfadt)(2)] salt, each CN moiety of the [Ni(tfadt)(2)](2)(-) dianion is coordinated to a (18-crown-6)Na(+) cation through a CN...Na interaction [N...Na = 2.481(3) A], affording an "axle

  由相应的环状二硫代碳酸酯制备新的1，2-二硫代酸酯配体，即2-（三氟甲基）丙烯腈-1,2-二硫代酸酯，在此缩写为tfadt。将这个被CN和CF（3）基团取代的配体与众所周知的马来腈-和双（三氟甲基）乙烷-1，2-二硫代酸酯进行比较。方形平面镍络合物的制备，电化学性质和X射线晶体结构，在它们的双阴离子抗磁性[Ni（tfadt）（2）]（2）（-）和单阴离子顺磁性[Ni（tfadt）（ 2）]（*）（-）形式报道，分别为n-Bu（4）N（+），PPh（4）（+）和（18-crown-6）Na（+）盐。在[（18-crown-6）Na]（2）[Ni（tfadt）（2）]盐中，[Ni（tfadt）（2）]（2）（-）二价阴离子的每个CN部分均与通过CN ... Na相互作用[N ... Na = 2.481（3）A]的（18-crown-6）Na（+）阳离子，提供了“带有车轮的车轴”模型，其中两个
• Perylene salts of unsymmetrical nickel and gold dithiolene complexes with 3 ? 2 stoichiometry: conformational polymorphism and strong antiferromagnetic interactions
  作者：Olivier Jeannin、Marc Fourmigu?

  DOI：10.1039/b608420f

  日期：——

  The square-planar AuIII complex of the unsymmetrical tfadt dithiolate ligand (tfadt: 2-(trifluoromethyl)acrylonitrile-1,2-dithiolate) is found to exhibit conformational polymorphism in its n-Bu4N+ salt, as both cis and trans isomers were found to crystallize separately in the same crystallization batch. Electrocrystallization of perylene in the presence of the diamagnetic [n-Bu4N][Au(tfadt)2] or the paramagnetic (S = 1/2) [n-Bu4N][Ni(tfadt)2] nickel analog affords isostructural salts with an unusual 3 ∶ 2 stoichiometry, that is [Per]3[M(tfadt)2]2 (M = Au, Ni), with an alternation of dicationic [Per]32+ perylene triads and dianionic [M(tfadt)2]22− dithiolene complex dyads within one-dimensional chains. These salts are characterized by strong antiferromagnetic interactions within perylene triads and [Ni(tfadt)2]22− dyads and an essentially diamagnetic behaviour.

  不对称tfadt二硫代配体（tfadt：2-（三氟甲基）丙烯腈-1,2-二硫代配体）的正方平面AuIII复合物在其n-Bu4N+盐中表现出构象多态性，因为在同一结晶批次中分离结晶出了顺式和反式异构体。用无磁性的[n-Bu4N][Au(tfadt)2]或顺磁性的（S = 1/2）[n-Bu4N][Ni(tfadt)2]镍同类化合物的电结晶法生成了具有不寻常3:2化学计量比的等结构盐，即[Per]3[M(tfadt)2]2（M = Au, Ni），在一维链中交替出现二阳离子[Per]32+的芘三聚体和二阴离子[M(tfadt)2]22-的二硫代烯配体二聚体。这些盐的特征是芘三聚体与[Ni(tfadt)2]22-二聚体之间强反铁磁相互作用，以及本质上的无磁行为。
• Ferromagnetic Interactions in Heterobimetallic Chains Formed through the Secondary Coordination of Dithiolene Complexes
  作者：Olivier Jeannin、Rodolphe Clérac、Thomas Cauchy、Marc Fourmigué

  DOI：10.1021/ic801343b

  日期：2008.11.17

  dithiolene complex based on the tfadt ligand (tfadt: 3-trifluoromethyl-acrylonitrile-2,3-dithiolate) is prepared as its n-Bu 4N (+) salt and crystallized with [Ni(cyclam)] (2+) into infinite, one-dimensional chains through CN...Ni interactions, avoiding any direct (antiferromagnetic) overlap between the dithiolene complexes. An unprecedented ferromagnetic interaction within the heterobimetallic chains

  基于tfadt配体（tfadt：3-三氟甲基-丙烯腈-2,3-dithiolate）的新型顺磁性（S = 1/2）铜二硫辛烯络合物被制备为其正丁基4N（+）盐，并用[Ni]结晶。 （cyclam）]（2+）通过CN ... Ni相互作用形成无限的一维链，从而避免了二硫醚配合物之间的任何直接（反磁性）重叠。观察到S = 1/2 [Cu（tfadt）2]（2-）和S = 1 [Ni（cyclam）]（2+）构造之间的异双金属链中前所未有的铁磁相互作用，尽管事实是[Cu（tfadt）2]（2-）（具有dx（2）-y（2）对称性）和[Ni（cyclam）]（2+）（具有dx（2）-y（2）和dz（2）对称）具有相同的对称性。根据磁化率的拟合推导实验交换相互作用（J exp / k B = +5。