bis[o-(trifluoromethyl)phenyl]dithiophosphinate | 930765-00-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: bis[o-(trifluoromethyl)phenyl]dithiophosphinate
• 英文别名: bis(o-trifluoromethylphenyl)dithiophosphinic acid；sulfanyl-sulfanylidene-bis[2-(trifluoromethyl)phenyl]-λ5-phosphane
• CAS: 930765-00-7
• 化学式: C₁₄H₉F₆PS₂
• 分子量: 386.322
• InChiKey: DWIFTDYUOZZLPO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.5
• 重原子数：
  23
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  33.1
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  nickel(II) sulphate 、 bis[o-(trifluoromethyl)phenyl]dithiophosphinate 生成 nickel(2+);sulfanylidene-sulfido-bis[2-(trifluoromethyl)phenyl]-λ5-phosphane
  参考文献：
  名称：

  二硫代次膦酸对镧系元素中Act系元素的高选择性分离：萃取，络合和DFT计算的深入研究

  摘要：

  为了进一步揭示了在由二硫代酸（DPAHs）镧系元素三价锕系元素的选择性分离的提取模型，用不同的取代基五个有代表性的配体DPAH已经合成，和它们的提取和络合行为朝向上午3+ / EU 3+已经研究无论是实验上还是理论上。将吸电子基团-CF 3引入DPAH配体中有利于它们在五个配体中的可萃取性。斜率分析表明，Am 3+和Eu 3+提取物是带有DPAH配体的四缔合物种。此外，从发光光谱，拉曼光谱和ESI-MS获得的结果表明，所有五个DPAH均与Eu 3+协同作用，主要以ML 3（HL）（H 2 O）的形式出现（L代表去质子化的DPAH） 。对热力学参数的密度泛函理论（DFT）计算表明，DPAH的可萃取性主要受这些配体的去质子化性质影响。同时，分子轨道分析表明，与Eu 3+相比，Am 3+的未占据价态轨道对硫孤电子对的亲合力更强。，这应该是DPAH配体对Am 3+相对Eu 3+的优异选择性的关键因素之一。

  DOI：

  10.1021/acs.inorgchem.8b01635
• 作为产物：
  描述：

  在 sodium hydrogen sulfide 作用下， 以 乙醚 为溶剂， 反应 24.0h， 生成 bis[o-(trifluoromethyl)phenyl]dithiophosphinate
  参考文献：
  名称：

  二硫代次膦酸对镧系元素中Act系元素的高选择性分离：萃取，络合和DFT计算的深入研究

  摘要：

  为了进一步揭示了在由二硫代酸（DPAHs）镧系元素三价锕系元素的选择性分离的提取模型，用不同的取代基五个有代表性的配体DPAH已经合成，和它们的提取和络合行为朝向上午3+ / EU 3+已经研究无论是实验上还是理论上。将吸电子基团-CF 3引入DPAH配体中有利于它们在五个配体中的可萃取性。斜率分析表明，Am 3+和Eu 3+提取物是带有DPAH配体的四缔合物种。此外，从发光光谱，拉曼光谱和ESI-MS获得的结果表明，所有五个DPAH均与Eu 3+协同作用，主要以ML 3（HL）（H 2 O）的形式出现（L代表去质子化的DPAH） 。对热力学参数的密度泛函理论（DFT）计算表明，DPAH的可萃取性主要受这些配体的去质子化性质影响。同时，分子轨道分析表明，与Eu 3+相比，Am 3+的未占据价态轨道对硫孤电子对的亲合力更强。，这应该是DPAH配体对Am 3+相对Eu 3+的优异选择性的关键因素之一。

  DOI：

  10.1021/acs.inorgchem.8b01635

文献信息

• METHOD FOR FORMING AN EXTRACTION AGENT FOR THE SEPARATION OF ACTINIDES FROM LANTHANIDES
  申请人：Klaehn John R.

  公开号：US20100094042A1

  公开（公告）日：2010-04-15

  An extraction agent for the separation of trivalent actinides from lanthanides in an acidic media and a method for forming same are described, and wherein the methodology produces a stable regiospecific and/or stereospecific dithiophosphinic acid that can operate in an acidic media having a pH of less than about 7.

  描述了一种用于在酸性介质中分离三价锕系元素和镧系元素的萃取剂，以及形成该萃取剂的方法，其中该方法产生了一种稳定的在酸性介质中可以操作的具有特定位置和/或立体特异性的二硫代膦酸。
• “Sweeping” Ortho Substituents Drive Desolvation and Overwhelm Electronic Effects in Nd³⁺ Chelation: A Case of Three Aryldithiophosphinates
  作者：Ning Pu、Jing Su、Lei Xu、Taoxiang Sun、Enrique R. Batista、Jing Chen、Ping Yang、Jenifer C. Shafer、Chao Xu

  DOI：10.1021/acs.inorgchem.9b01931

  日期：2020.1.6

  -CF3-derivatized aryldithiophosphinates have not been considered to date. This systematic study considers the complexation of three CF3-substituted aryldithiophosphinates-bis(phenyl)dithiophosphinate (LI), [o-(trifluoromethyl)phenyl](phenyl)dithiophosphinate (LII), and bis[o-(trifluoromethyl)phenyl]dithiophosphinate (LIII), with Nd3+ in an ethanolic environment. The chelating ability of NdIII by these ligands follows

  双[邻-（三氟甲基）苯基]二硫代次膦酸酯是一种能够提供最大的三价镧系元素（Ln3 +）-act系元素（An3 +）分离因子的给硫配体。文献表明，-CF3官能团在芳族环上最接近连接硫原子的位置和数量会显着影响Ln3 + -An3 +的萃取和分离因子，但迄今为止尚未考虑过- -衍生的芳基二硫代次膦酸酯的络合热力学。 。该系统研究考虑了 取代的芳基二硫代次膦酸酯-双（苯基）二硫代次膦酸酯（LI），[邻-（三氟甲基）苯基]（苯基）二硫代次膦酸酯（LII）和双[o-（三氟甲基）苯基]二硫代次膦酸酯（ LIII），在乙醇环境中使用Nd3 +。这些配体对NdIII的螯合能力遵循LIII> LII> LI的顺序，这与报道的提取效率相符。正ΔS以及正ΔH均表明Nd3 +螯合是熵驱动的，有效的去溶剂化对于使Nd3 +与弱相互作用的含硫配体相互作用至关重要。扩展的X射线吸收精细结构结果证实了热力学研究，并暗示LI最多只能与Nd3
• Probing Ni[S₂PR₂]₂ Electronic Structure to Generate Insight Relevant to Minor Actinide Extraction Chemistry
  作者：Scott R. Daly、Jason M. Keith、Enrique R. Batista、Kevin S. Boland、Stosh A. Kozimor、Richard L. Martin、Brian L. Scott

  DOI：10.1021/ic3001587

  日期：2012.7.16

  A method to evaluate the electronic structure of minor actinide extractants is described. A series of compounds containing effective and ineffective actinide extractants (dithiophosphinates, S2PR2-) bound to a common transition metal ion (Ni2+) was analyzed by structural, spectroscopic, and theoretical methods. By using a single transition metal that provides structurally similar compounds, the metal contributions to bonding are essentially held constant so that subtle electronic variations associated with the extracting ligand can be probed using UV-vis spectroscopy. By comparison, it is difficult to obtain similar information using analogous techniques with minor actinide and lanthanide complexes. Here, we demonstrate that this approach, supplemented with ground state and time-dependent density functional theory, provides insight for understanding why high separation factors are reported for the extractant HS2P(o-CF3C6H4)(2), while lower values are reported and anticipated for other HS2PR2 derivatives (R = C6H5, p-CF3C6H4, m-CF3C6H4). The implications of these results for correlating electronic structure with the selectivity of HS2PR2 extractants are discussed.
• Bis(o-trifluoromethylphenyl)dithiophosphinic methyl ester
  作者：John R. Klaehn、Dean R. Peterman、Mason K. Harrup、Thomas A. Luther、Lee M. Daniels

  DOI：10.1016/j.ica.2011.01.023

  日期：2011.5

  When bis(o-trifluoromethylphenyl) dithiophosphinic acid (1) is dissolved in methanol, crystals of bis(o-trifluoromethylphenyl) dithiophosphinic methyl ester (2) are formed. The structure of dithiophosphinic methyl ester (2) has been characterized via single-crystal X-ray diffraction and multinuclear NMR studies. Compound 2 is remarkable in that the dithiophosphinic (PS(2)) core is preserved during this transformation. The transformation to 2 suggests that the o-trifluoromethylphenyl groups on phosphorus assist in retaining the PS(2) core, possibly by steric hindrance. Published by Elsevier B. V.
• ACTINIDE EXTRACTION METHODS AND ACTINIDE SEPARATION COMPOSITIONS
  申请人：Peterman Dean R.

  公开号：US20100150798A1

  公开（公告）日：2010-06-17

  Methods of separating actinides from lanthanides are disclosed. A regio-specific/stereo-specific dithiophosphinic acid having organic moieties is provided in an organic solvent that is then contacted with an acidic medium containing an actinide and a lanthanide. The method can extend to separating actinides from one another. Actinides are extracted as a complex with the dithiophosphinic acid. Separation compositions include an aqueous phase, an organic phase, dithiophosphinic acid, and at least one actinide. The compositions may include additional actinides and/or lanthanides. A method of producing a dithiophosphinic acid comprising at least two organic moieties selected from aromatics and alkyls, each moiety having at least one functional group is also disclosed. A source of sulfur is reacted with a halophosphine. An ammonium salt of the dithiophosphinic acid product is precipitated out of the reaction mixture. The precipitated salt is dissolved in ether. The ether is removed to yield the dithiophosphinic acid.