(+/-)-diphenyl([2.2]paracyclophan-4-yl)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: (+/-)-diphenyl([2.2]paracyclophan-4-yl)phosphine
• 英文别名: 4-diphenylphosphine[2.2]paracyclophane；rac-diphenyl[2.2]paracyclophanylphosphine；diphenyl[2.2]paracyclophanylphosphine；diphenyl(5-tricyclo[8.2.2.24,7]hexadeca-1(13),4,6,10(14),11,15-hexaenyl)phosphane
• 化学式: C₂₈H₂₅P
• 分子量: 392.48
• InChiKey: MANFHYIGAACNLA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.1
• 重原子数：
  29
• 可旋转键数：
  3
• 环数：
  8.0
• 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：
  0

反应信息

• 作为反应物：
  描述：

  (+/-)-diphenyl([2.2]paracyclophan-4-yl)phosphine 、 顺-二氯二(吡啶)铂(II) 以 二氯甲烷 为溶剂， 以85%的产率得到
  参考文献：
  名称：

  弱氢键和所含溶剂对方平面复合反式-Pt {PPh 2（C 16 H 15）} 2 Cl 2的晶体结构的影响

  摘要：

  从二氯甲烷-乙醚（1：1）中结晶出正方形平面的反式-Pt {PPh 2（C 16 H 15）} 2 Cl 2复合物，得到了两种不同的溶剂化物。反式-Pt {PPh 2（C 16 H 15）} 2 Cl 2 ·CH 2 Cl 2 1和反式-Pt {PPh 2（C 16 H 15）} 2 Cl 2 ·Et 2 O 2；CH 2 Cl2与配合物形成氢键相互作用，而Et 2 O仅参与弱范德华相互作用。这些差异是由于每种溶剂的氢键键合特性不同而引起的。

  DOI：

  10.1039/a807483f
• 作为产物：
  描述：

  对二甲苯二聚体 在 正丁基锂 、 溴 、 铁粉 作用下， 以 四氢呋喃 、 四氯化碳 为溶剂， 反应 7.5h， 生成 (+/-)-diphenyl([2.2]paracyclophan-4-yl)phosphine
  参考文献：
  名称：

  亚胺的无金属催化加氢与可回收的[2.2]环芳烃衍生的失意路易斯对催化剂

  摘要：

  合成了一系列具有可逆的，无金属的氢活化作用的[2.2]对环芳基衍生的失意的Lewis对（FLP），并成功地以中等到良好的产率将其用于亚胺的氢化。新型FLP系统的高稳定性可有效回收无金属催化剂。该反应也可能具有较大的相容性，并已发展为西那卡塞{{ R } -N- [1-（1-萘基）乙基] -3- [3-（三氟甲基）苯基]丙烷-1-胺}，没有重金属残留物。

  DOI：

  10.1002/adsc.201301007

文献信息

• Metal‐to‐Metal Distance Modulated Au(I)/Ru(II) Cyclophanyl Complexes: Cooperative Effects in Photoredox Catalysis
  作者：Christoph Zippel、Roumany Israil、Lars Schüssler、Zahid Hassan、Erik K. Schneider、Patrick Weis、Martin Nieger、Claudia Bizzarri、Manfred M. Kappes、Christoph Riehn、Rolf Diller、Stefan Bräse

  DOI：10.1002/chem.202102341

  日期：2021.11.2

  The modular synthesis of Au(I)/Ru(II) decorated mono- and heterobimetallic complexes with π-conjugated [2.2]paracyclophane is described. [2.2]Paracyclophane serves as a rigid spacer which holds the metal centers in precise spatial orientations and allows metal-to-metal distance modulation. A broad set of architectural arrangements of pseudo -geminal, -ortho, -meta, and -para substitution patterns were

  描述了 Au(I)/Ru(II) 修饰的单金属和异双金属配合物与 π 共轭[2.2]对环芳烷的模块化合成。 [2.2]对环芳烷用作刚性间隔物，将金属中心保持在精确的空间方向并允许金属到金属的距离调制。采用了一系列广泛的伪双子、邻位、间位和对位取代模式的架构安排。 Au(I)/Ru(II)异双金属配合物的金属间距离调节和环芳基支架固有的跨环π通讯为研究构效关系和协同效应提供了一个有前景的平台。 Au(I)/Ru(II) 异双金属环芳基配合物稳定、易于制备，并且在可见光促进的芳基化 Meyer-Schuster 重排中表现出良好的催化活性。
• Synthesis of planar chiral [2.2]paracyclophane monophosphine ligands and their application in the umpolung allylation of aldehydes
  作者：Tang-Zhi Zhang、Li-Xin Dai、Xue-Long Hou

  DOI：10.1016/j.tetasy.2007.01.020

  日期：2007.2

  Chiral [2.2]paracyclophane monophosphines 8 were synthesized via resolution using chiral palladacycle 10. Chiral phosphinite 5 was also prepared from 4-hydroxy[2.2]paracyclophane. Phosphines 8 and phosphinite 5 were used as the ligand in the umpolung allylation of aldehydes 14 with cyclohexenyl acetate 15, giving homoallyl alcohols 16 in high diastereoselectivity and in moderate to good enantioselectivity. Palladacycle 10 was recovered by treating the palladacycle-phosphine complexes with sodium prolinate, followed by treatment with HCl in high yield. (c) 2007 Elsevier Ltd. All rights reserved.
• Chemical, Electrochemical, and Structural Aspects of the Ruthenium Complexes Ru(η-arene)Cl₂(P) (Where Arene = Benzene, [2.2]Paracyclophane and P = Triphenylphosphine, <i>rac</i>-[2.2]Paracyclophanylphosphine)
  作者：Rajiv Bhalla、Clive J. Boxwell、Simon B. Duckett、Paul J. Dyson、David G. Humphrey、Jonathan W. Steed、Priya Suman

  DOI：10.1021/om010763a

  日期：2002.3.1

  Reaction of diphenyl[2.2]paracyclophanylphosphine, rac-PPh2(C16H15) (1), with [Ru(eta-arene)Cl-2](2) (where arene = C6H6, [2.2]paracyclophane (C16H16)) in a 2:1 ratio affords the half-sandwich complexes Ru(eta-arene)Cl-2(PPh2(C16H15)) (arene = C6H6 (2), C16H16 (3)) in high yield. In solution, the structures of 2 and 3 have been probed and assigned using 2D NMR spectroscopy and the structure of the [2.2]paracyclophane derivative, 3, has been established in the solid-state by single-crystal X-ray diffraction. Cyclic voltammetry and steady-state voltammetry of 2 in 0.25 M [(Bu4N)-Bu-n] [PF6]/CH2Cl2 shows that the complex undergoes a chemically reversible, one-electron oxidation and an irreversible, two-electron reduction. The voltammetry of the related complex [Ru(eta(6)-C6H6)Cl-2(PPh3)] (4), recorded under analogous conditions, is similar both in terms of the processes displayed and the potentials at which they occur.
• On the products obtained from reaction of rac-diphenyl[2.2]para-cyclophanylphosphine with (cycloocta-1,5-diene)palladium(II)chloride
  作者：Damir Blazina、Simon B Duckett、Paul J Dyson、Rosario Scopelliti、Jonathan W Steed、Priya Suman

  DOI：10.1016/s0020-1693(03)00464-x

  日期：2003.10

  The reaction of Pd(cod)Cl-2 (cod = cycloocta-1,5-diene) with 1 and 2 equiv. of rac-diphenyl[2.2]paracyclophanylphosphine, rac-PPh2(C16H15), affords the dimer [PdPPh2(C16H15)}Cl-2](2) (1) and the square-planar complex trans-PdPPh2(C16H15)}(2)Cl-2 (2), respectively. In solution the dimer undergoes a fluxional process which has been probed by NMR and involves isomerisation between pseudo-trans- and cis-conformations. The structures of trans -[PdPh-2(C16H15)}Cl-2](2) (1a) and 2 have been established by single crystal X-ray diffraction; the structure of the dimer is severely disordered. In addition, co-crystals containing both these complexes and solvate molecules have been isolated and their structures established by single crystal X-ray diffraction. The structure of the monomer in the homonuclear and co-crystals are not too dissimilar whereas the structure the dimer has a significantly different structure in the homonuclear and co-crystals. In the homonuclear crystal the central Pd2Cl2 unit has a dihedral angle of 26.5degrees between the two planes whereas the Pd2Cl2 unit in the co-crystals is planar. (C) 2003 Elsevier B.V. All rights reserved.
• A remarkable example of co-crystallisation: the crystal structure of the mononuclear and dinuclear diphenyl[2.2]paracyclophanylphosphine palladium(II) chloride complexes trans-[Pd{PPh2(C16H15)}2Cl2]·[Pd{PPh2(C16H15)}Cl2]2·0.6CH2Cl2
  作者：Philip W. Dyer、Paul J. Dyson、Stuart L. James、Priya Suman、Philip W. Dyer、John E. Davies、Caroline M. Martin

  DOI：10.1039/a801863d

  日期：——

  The reaction of [Pd(cod)Cl2] (cod = cycloocta-1,5-diene) with rac-diphenyl[2.2]paracyclophanylphosphine PPh2(C16H15) affords trans-[PdPPh2(C16H15)}2Cl2] and [PdPPh2(C16H15)}Cl2]2 in approximately equal yield which co-crystallise to form an unusual solid-state material.