chlorobis(2-(trifluoromethyl)phenyl)phosphine

• 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: chlorobis(2-(trifluoromethyl)phenyl)phosphine
• 英文别名: Phosphinous chloride, bis[2-(trifluoromethyl)phenyl]-；chloro-bis[2-(trifluoromethyl)phenyl]phosphane
• 化学式: C₁₄H₈ClF₆P
• 分子量: 356.635
• InChiKey: OKHYKWKIMSLFLA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  22
• 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：
  0
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  chlorobis(2-(trifluoromethyl)phenyl)phosphine 在 LiAlH 作用下， 以 乙醚 为溶剂， 生成 Bis-(2-trifluoromethyl-phenyl)-phosphane
  参考文献：
  名称：

  Electron Withdrawing Substituents on Equatorial and Apical Phosphines Have Opposite Effects on the Regioselectivity of Rhodium Catalyzed Hydroformylation

  摘要：

  The electronic effects of electron withdrawing aryl substituents on equatorial and apical diphosphines were investigated. Chelating diphosphines designed to coordinate in diequatorial or in apical-equatorial positions were synthesized, and their effects on the regioselectivity of rhodium catalyzed 1-hexene hydroformylation were observed. Only diequatorial coordination was observed for 2,2'-bis[(diphenylphosphino)methyl]-1,1'-biphenyl (BISBI) complexes (BISBI)Ir(CO)(2)H (8) and [BISBI-(3,5-CF3)]Ir(CO)(2)H (10), and only apical-equatorial coordination was seen for 1,2-bis(diphenylphosphino)ethane (DIPHOS) complexes (DIPHOS)Ir(CO)(2)H (14) and [DIPHOS-(3,5-CF3)]Ir(CO)(2)H (15). For the trans-1,2-bis [(diphenylphosphino)methyl] cyclopropane (T-BDCP) complexes, a mixture of diequatorial and apical-equatorial complexes was seen. For (T-BDCP)Ir(CO)(2)H (12), 12-ee was favored over 12-ee by 63:37, but for [T-BDCP-(3,5-CF3)]Ir(CO)(2)H (13) the conformational preference was reversed and a 10:90 ratio of 13-ee:13-ee was seen. The electron withdrawing groups in the equatorial positions of BISBI-(3,5-CF3) (1) and T-BDCP-(3,5-CF3) (2) led to an increase in n-aldehyde regioselectivity in rhodium catalyzed hydroformylation. However, electron withdrawing aryl substituents in the apical positions of DIPHOS-(3,5-CF3) (3) led to a decrease in n-aldehyde regioselectivity in rhodium catalyzed hydroformylation.

  DOI：

  10.1021/ja9719440
• 作为产物：
  描述：

  邻溴三氟甲苯 在 正丁基锂 、 二乙基二氯磷 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 3.0h， 以91%的产率得到chlorobis(2-(trifluoromethyl)phenyl)phosphine
  参考文献：
  名称：

  立体选择性丙烯酸酯插入的概念

  摘要：

  各种膦磺酸基配体和相应的钯配合物 [{((P^O)PdMeCl)-μ-M}(n)] ([{((X)1-Cl)-μ-M}(n)], (P ^O) = κ(2)-P,O-Ar(2)PC(6)H(4)SO(2)O) 对称 (Ar = 2-MeOC(6)H(4), 2-CF (3)C(6)H(4), 2,6-(MeO)(2)C(6)H(3), 2,6-(iPrO)(2)C(6)H(3), 2-(2',6'-(MeO)(2)C(6)H(3))C(6)H(4)) 和不对称取代的磷原子 (Ar(1) = 2,6-(MeO) )(2)C(6)H(3)，Ar(2) = 2'-(2,6-(MeO)(2)C(6)H(3))C(6)H(4)；合成了 Ar(1) = 2,6-(MeO)(2)C(6)H(3)、Ar(2) = 2-cHexOC(6)H(4))。通过变温 NMR 研究和线形分析对自由配体和配合物进行分子运动和动力学分析。ΔG(‡)

  DOI：

  10.1021/ja3101787

文献信息

• A Fluorescence-Based Assay for High-Throughput Screening of Coupling Reactions. Application to Heck Chemistry
  作者：Kevin H. Shaughnessy、Paul Kim、John F. Hartwig

  DOI：10.1021/ja983419m

  日期：1999.3.1

  A new fluorescence-based assay for high-throughput screening of reactions that couple two organic molecules is described. The assay involves reaction of one substrate containing a tethered fluorophore with a second molecule that is attached to a solid support. A successful coupling process is signaled by fluorescence of the solid support, which can be isolated by either simple centrifugation or filtration

  描述了一种新的基于荧光的检测，用于对结合两个有机分子的反应进行高通量筛选。该测定涉及一种含有系留荧光团的底物与附着在固体支持物上的第二种分子的反应。成功的偶联过程是由固体支持物的荧光发出的信号，可以通过简单的离心或过滤来分离。为了在当前激烈的研究中在催化过程的背景下评估该测定，我们寻找改进的、易于获得的膦用于 Heck 化学。将含有系链香豆素的丙烯酸酯与负载在交联聚苯乙烯树脂上的芳基卤反应。将我们基于荧光的测定结果与连续 GC 分析的结果进行比较表明，基于荧光的测定准确地选择了最活跃的配体，用于芳基溴化物和氯化物的 Heck 偶联。测定选择的两个配体，三（叔丁基）膦和二（叔丁基膦）...
• 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。
• Highly Selective Separation of Actinides from Lanthanides by Dithiophosphinic Acids: An in-Depth Investigation on Extraction, Complexation, and DFT Calculations
  作者：Zhipeng Wang、Ning Pu、Yin Tian、Chao Xu、Fang Wang、Ying Liu、Lirong Zhang、Jing Chen、Songdong Ding

  DOI：10.1021/acs.inorgchem.8b01635

  日期：2019.5.6

  To further reveal the extraction model for selective separation of trivalent actinides over lanthanides by dithiophosphinic acids (DPAHs), five representative DPAH ligands with different substituent groups have been synthesized, and their extraction and complexation behaviors toward Am3+/Eu3+ have been investigated both experimentally and theoretically. The introduction of electron-withdrawing group

  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。
• Differentiation between Chelate Ring Inversion and Aryl Rotation in a CF₃-Substituted Phosphine-Sulfonate Palladium Methyl Complex
  作者：Ge Feng、Matthew P. Conley、Richard F. Jordan

  DOI：10.1021/om500699t

  日期：2014.9.8

  1H–19F nuclear Overhauser effects. In CD2Cl2 solution in the temperature range of −80 to 20 °C, 3 adopts an exo2 conformation. One o-CF3-Ph ring is positioned such that the CF3 group points toward Pd (exo) and exhibits through-space 4JPF coupling. The other o-CF3-Ph ring is positioned such that the CF3 group points away from Pd (endo) and does not exhibit through-space 4JPF coupling, and the o-H lies in

  CF 3取代的（正膦基芳烃磺酸盐）Pd配合物（PO-CF 3）PdMe（L）（[PO-CF 3 ] - = 2-（o -CF 3 -Ph）2 P} -4-Me-苯磺酸盐，L = 2,6-二甲基吡啶（3），吡啶（4））已通过NMR光谱法进行了研究，特别利用了31 P– 19 F的空间耦合和1 H– 1 H和1 H- 19 F核Overhauser效应。在CD 2中Cl 2溶液在-80至20°C的温度范围内，3采用exo 2构象。放置一个o -CF 3 -Ph环，使CF 3基团指向Pd（exo），并表现出贯穿空间4 J PF耦合。另一个o -CF 3 -Ph环的位置应使CF 3基团指向远离Pd（内）且不表现出贯穿空间4 J PF耦合，并且o-H位于Pd正方形平面的轴向位置附近的屏蔽区域中，并且表现出低场化学位移（δ> 9）。络合物4在-90°C下以exo 2和exo 3异构体的2：1混合物形式存在于CD
• Palladium-Catalyzed Synthesis of Pure, Regiodefined Polymeric Triarylamines
  作者：Felix E. Goodson、Sheila I. Hauck、John F. Hartwig

  DOI：10.1021/ja990632p

  日期：1999.8.1

  Triarylamine polymers were prepared by palladium-catalyzed amination of aryl halides, and the electrochemical and magnetic properties of these materials were studied. Through a careful evaluation of the catalytic and polymer chemistry involved in this process, triarylamine polymers that are exclusively linear and free of phosphorus impurity in the polymer chain have been prepared. To suppress molecular

  通过钯催化的芳基卤化物胺化制备了三芳胺聚合物，并研究了这些材料的电化学和磁性能。通过对该过程中涉及的催化和聚合物化学的仔细评估，已经制备出聚合物链中完全线性且不含磷杂质的三芳基胺聚合物。为了抑制钯催化的聚（N-芳基苯胺）聚合反应的分子量限制副反应，在小分子形成三芳胺的反应中筛选了许多膦。在这些膦中，三（邻甲氧基甲基苯基）膦（7）和三（叔丁基）膦（8）导致定量胺化，无需配体芳基化、芳基溴加氢脱卤或膦芳基与芳基溴的交换。