4,13-bis(diphenylphosphanyl)-[2.2]paracyclophane | 1345160-39-5

• 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: 4,13-bis(diphenylphosphanyl)-[2.2]paracyclophane
• 英文别名: 4,13-bis-(diphenylphosphino)-[2.2]paracyclophane；4,13-bis(diphenylphosphino)[2.2]paracyclophane；GemPhos；(12-Diphenylphosphanyl-5-tricyclo[8.2.2.24,7]hexadeca-1(12),4,6,10,13,15-hexaenyl)-diphenylphosphane
• CAS: 1345160-39-5
• 化学式: C₄₀H₃₄P₂
• 分子量: 576.657
• InChiKey: QLWSVCLEYVUUPS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.8
• 重原子数：
  42
• 可旋转键数：
  6
• 环数：
  10.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  4,13-bis(diphenylphosphanyl)-[2.2]paracyclophane 在 selenium 作用下， 以 氯仿 为溶剂， 反应 5.0h， 生成 4,13-bis(diphenylphosphino)[2.2]paracyclophane bisselenide
  参考文献：
  名称：

  Coupling of ortho-substituted aryl chlorides with bulky amides

  摘要：

  大量的酰胺与失活的、立体受阻的芳基氯化物偶联，产生了迄今为止过渡金属催化无法有效获得的产物。非对称双膦配体的应用是实现高催化活性的关键。

  DOI：

  10.1039/c1cc14844c
• 作为产物：
  描述：

  4-bromo-15-diphenylphosphonyl[2.2]paracyclophane 在 tetraphosphorus decasulfide 、 叔丁基锂 、 亚磷酸三乙酯 作用下， 以 四氢呋喃 、 氯苯 、 正戊烷 为溶剂， 反应 26.0h， 生成 4,13-bis(diphenylphosphanyl)-[2.2]paracyclophane
  参考文献：
  名称：

  Coupling of ortho-substituted aryl chlorides with bulky amides

  摘要：

  大量的酰胺与失活的、立体受阻的芳基氯化物偶联，产生了迄今为止过渡金属催化无法有效获得的产物。非对称双膦配体的应用是实现高催化活性的关键。

  DOI：

  10.1039/c1cc14844c
• 作为试剂：
  描述：

  二苯甲基硅烷 、 右旋香芹酮 在 4,13-bis(diphenylphosphanyl)-[2.2]paracyclophane 、 三(五氟苯基)硼烷 、 氢气 作用下， 以 甲苯 为溶剂， 反应 48.0h， 生成 (1R,2S,5S)-2-methyl-5-(prop-1-en-2-yl)cyclohexyloxy(methyl)-diphenylsilane 、 (1S,2R,5S)-2-methyl-5-(prop-1-en-2-yl)cyclohexyloxy(methyl)-diphenylsilane
  参考文献：
  名称：

  [2.2]Paracyclophane derived bisphosphines for the activation of hydrogen by FLPs: application in domino hydrosilylation/hydrogenation of enones

  摘要：

  描述了两种[2.2]对环苯烃衍生的双磷烯（1、2a和2b）与三（五氟苯基）硼烷（3）在室温下进行氢的异裂。相应的受挫路易斯对（FLPs）在氢的活化过程中表现出不同的行为。这是由于双磷烯的立体和电子性质各不相同。受挫路易斯对的反应性在首个催化FLPs的非对映选择性多米诺氢硅化/氢化反应中得到了利用。

  DOI：

  10.1039/c2dt30374d

文献信息

• [2.2]Paracyclophanediyldiphosphane Complexes of Gold
  作者：Christian Sarcher、Anja Lühl、Florian C. Falk、Sergei Lebedkin、Michael Kühn、Cong Wang、Jan Paradies、Manfred M. Kappes、Wim Klopper、Peter W. Roesky

  DOI：10.1002/ejic.201200751

  日期：2012.11

  We have prepared digold(I) complexes with the rigid-backbone diphosphane ligands PhanePhos, xyl-PhanePhos, and Ph2-GemPhos. All complexes were characterized by single-crystal X-ray diffraction, NMR, IR, Raman, and photoluminescence (PL) spectroscopy. [PhanePhos(AuCl)2] and [GemPhos(AuCl)2] show a very similar ligand scaffold, but different (aurophilic vs. nonaurophilic) intramolecular Au–Au distances

  我们已经制备了具有刚性骨架二膦配体 PhanePhos、xyl-PhanePhos 和 Ph2-GemPhos 的 digold(I) 配合物。所有配合物均通过单晶 X 射线衍射、核磁共振、红外、拉曼和光致发光 (PL) 光谱表征。[PhanePhos(AuCl)2] 和 [GemPhos(AuCl)2] 显示出非常相似的配体支架，但不同（亲金与非亲金）分子内 Au-Au 距离。两种化合物的吸收光谱和 PL 光谱非常相似。理论研究表明激发态具有不同的特性（即受金-金接触的影响）。然而，各自的跃迁能量彼此接近，因此产生相似的实验光谱。金原子似乎在电子弛豫动力学中产生了显着的重原子效应。因此，[PhanePhos(AuCl)2] 和 [GemPhos(AuCl)2] 在低温下都显示出亮绿色的毫秒长磷光，尽管后者在环境温度下被淬灭。[PhanePhos(AuCl)2] 和 [GemPhos(AuCl)2]
• Synthesis and photophysical properties of GemPhos noble metal complexes
  作者：Christian Sarcher、Sebastian Bestgen、Florian C. Falk、Sergei Lebedkin、Jan Paradies、Peter W. Roesky

  DOI：10.1016/j.jorganchem.2015.02.033

  日期：2015.10

  GemPhos, a diphosphine ligand with a rigid paracyclophane scaffold, was used to prepare complexes of the noble metals gold, palladium, and platinum. The reaction of GemPhos with [Au(tht)(2)][ClO4] (tht = tetrahydrothiophene) surprisingly yielded a mononuclear charge separated gold compound [(GemPhos) Au][ClO4], in which the gold atom exhibits an uncommon trigonal planar coordination geometry. Furthermore, similar palladium [(GemPhos) (PdCl2)] and platinum [(GemPhos)(PtCl2)] complexes were obtained in very good yields by the reaction of GemPhos with [MCl2(COD)] (M = Pd, Pt; COD = 1,5-cyclooctadiene) in hot DMSO. All compounds were fully characterized by analytical and spectroscopic techniques and their solid-state structures were established by single X-ray crystallography. Their photoluminescent properties were measured at low and ambient temperatures, revealing different behavior depending on the metal and coordination mode. (C) 2015 Elsevier B.V. All rights reserved.
• [2.2]Paracyclophane derived bisphosphines for the activation of hydrogen by FLPs: application in domino hydrosilylation/hydrogenation of enones
  作者：Lutz Greb、Pascual Oña-Burgos、Adam Kubas、Florian C. Falk、Frank Breher、Karin Fink、Jan Paradies

  DOI：10.1039/c2dt30374d

  日期：——

  The heterolytic splitting of hydrogen by two types of [2.2]paracyclophane derived bisphosphines (1, 2a and 2b) in combination with tris(pentafluorophenyl)borane (3) at room temperature is described. The corresponding frustrated Lewis pairs (FLPs) exhibit different behavior in the activation of hydrogen. This results from diverse steric and electronic properties of the bisphosphines. The reactivity of the frustrated Lewis pairs was exploited in the first diastereoselective domino hydrosilylation/hydrogenation reaction catalyzed by FLPs.

  描述了两种[2.2]对环苯烃衍生的双磷烯（1、2a和2b）与三（五氟苯基）硼烷（3）在室温下进行氢的异裂。相应的受挫路易斯对（FLPs）在氢的活化过程中表现出不同的行为。这是由于双磷烯的立体和电子性质各不相同。受挫路易斯对的反应性在首个催化FLPs的非对映选择性多米诺氢硅化/氢化反应中得到了利用。
• Coupling of ortho-substituted aryl chlorides with bulky amides
  作者：Florian C. Falk、Roland Fröhlich、Jan Paradies

  DOI：10.1039/c1cc14844c

  日期：——

  Voluminous amides were coupled with deactivated, sterically hindered aryl chlorides in excellent yields providing products, which have not been efficiently accessible by transition metal catalysis so far. Application of an unsymmetric bisphosphine ligand was critical for the high catalytic activity.

  大量的酰胺与失活的、立体受阻的芳基氯化物偶联，产生了迄今为止过渡金属催化无法有效获得的产物。非对称双膦配体的应用是实现高催化活性的关键。