Ph2P(CH2)2OPh | 162616-45-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: Ph2P(CH2)2OPh
• 英文别名: 2-Phenoxyethyl(diphenyl)phosphane
• CAS: 162616-45-7
• 化学式: C₂₀H₁₉OP
• 分子量: 306.344
• InChiKey: IKTGODOGWNPSSZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  22
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  Ph2P(CH2)2OPh 以 二氯甲烷 、 二氯甲烷-D2 、 乙腈 为溶剂， 生成 cis-[κ2-(Ph2PC2H4SMe)-κ1-(Ph2PC2H4OPh)Pd(acetonitrile)](BF4)2
  参考文献：
  名称：

  Reversible Ligand Pairing and Sorting Processes Leading to Heteroligated Palladium(II) Complexes with Hemilabile Ligands

  摘要：

  Halide-induced ligand pairing and sorting processes have been observed in the context of Pd(II) complexes with hemilabile P,S and P,O ligands. Mixing of the ligands Ph2PCH2CH2SMe (7) and Ph2PCH2CH2SPh (8) with a Pd(II) precursor in CH2Cl2 results in a mixture of [(7)(2)ClPd]Cl, [(8)(2)Cl2Pd], and [(7)(8)ClPd]Cl complexes at 20 degrees C. This equilibrium can be driven toward the heteroligated structure [(7)(8)ClPd]Cl by (1) cooling the mixture or (2) precipitation with hexanes, leading to the exclusive fort-nation of semiopen heteroligated complex cis-[kappa(2)-(7)-kappa(1)-(8)ClPd]Cl (9a), as confirmed by a single-crystal X-ray diffraction study and solid state CPMAS P-31{H-1} NMR spectroscopy. Dissolution of 9a in CH2Cl2 leads to the original mixture of complexes, which illustrates the reversible nature of this ligand pairing and sorting process. Similar processes occur when a combination of P,S and P,O ligands is used. The semiopen heteroligated complexes can be chemically manipulated in a reversible fashion to form closed complexes, allowing for control of the relative position and flexibility between neighboring substituents in these "tweezer"-like structures. Control experiments suggest these ligand sorting and pairing processes occur via a halide-induced ligand rearrangement (HILR) reaction.

  DOI：

  10.1021/om801060m
• 作为产物：
  描述：

  potassium diphenylphosphine 、 2-氯苯乙醚 以 四氢呋喃 为溶剂， 以70%的产率得到Ph2P(CH2)2OPh
  参考文献：
  名称：

  Singewald, Elizabeth T.; Mirkin, Chad A.; Levy, Allison D., Angewandte Chemie, 1994, vol. 106, # 23/24, p. 2524 - 2526

  摘要：

  DOI：

文献信息

• Catalyst-free hydrophosphination of alkenes in presence of 2-methyltetrahydrofuran: a green and easy access to a wide range of tertiary phosphines
  作者：Damien Bissessar、Julien Egly、Thierry Achard、Pascal Steffanut、Stéphane Bellemin-Laponnaz

  DOI：10.1039/c9ra04896k

  日期：——

  reaction that is free of base, acid and catalyst, using only 2-methyltetrahydrofuran as additive has been performed. A new family of mono-, di-, tri- and tetra-phosphines compounds are obtained in good to excellent yields by adding diphenylphosphine to alkenes, mono- and polyfunctional acrylics (based on acrylate and methacrylate motifs) and acrylamide substrates. Addition of four equivalent of bio-mass

  已经进行了不含碱、酸和催化剂的氢膦化反应，仅使用 2-甲基四氢呋喃作为添加剂。通过将二苯基膦添加到烯烃、单官能和多官能丙烯酸树脂（基于丙烯酸酯和甲基丙烯酸酯基体）和丙烯酰胺基材中，可以以良好至优异的产率获得一系列新的单、二、三和四膦化合物。将四当量的生物质衍生的 2-MeTHF 添加到反应介质中可以提高转化率和反应时间，并降低反应物对氧化的敏感性。这种简单、直接和原子经济的方法尊重绿色化学的原则。此外，在每种情况下，这种转化都显示出对反马尔科夫尼科夫产物的专有区域选择性。
• General Strategy for the Synthesis of Rigid Weak-Link Approach Platinum(II) Complexes: Tweezers, Triple-Layer Complexes, and Macrocycles
  作者：Robert D. Kennedy、Charles W. Machan、C. Michael McGuirk、Mari S. Rosen、Charlotte L. Stern、Amy A. Sarjeant、Chad A. Mirkin

  DOI：10.1021/ic302855f

  日期：2013.5.20

  (P,S–C6F4H) hemilabile ligand is used as the weakly chelating counterpart. The HILR reaction has also been used to synthesize bisplatinum(II) macrocycles free of oligomeric material without having to resort to the high-dilution conditions typical for macrocycle synthesis. This approach is complementary to the traditional WLA to the synthesis of macrocyclic complexes which typically proceeds via fully

  具有P，X–芳基半不稳定配体（P ^ = Ph 2 PCH 2 CH 2 –，X =硫醚或胺）的空气稳定的杂化铂（II）弱连接方法（WLA）镊子和三层复合物通过卤化物诱导的配体重排（HILR）反应，使用一锅法，部分氯化物吸收法合成了SnO2。该方法是通用的，可与多种基于膦的半不稳定配体一起使用。当P，S–Ph配体用作相对较强的螯合配体时，当以醚-（P，O-Ph），胺-（P，N-Ph 2）或氟化硫醚为基时，杂化的络合物会干净地形成（P，S–C 6 F 4H）半不稳定的配体用作弱螯合的对应物。HILR反应也已用于合成不含低聚物质的双铂（II）大环化合物，而不必诉诸于大环合成的典型高稀释条件。这种方法是传统WLA的补充，可以合成大环配合物，通常通过完全封闭的无氯中间体进行。可以通过氯化物的提取和添加在半开放的（只有一个螯合配体）和完全封闭的（两个配体都螯合）之间切换复合物的结构。
• Heteroligated RhI Tweezer Complexes
  作者：Aaron M. Brown、Maxim V. Ovchinnikov、Chad A. Mirkin

  DOI：10.1002/anie.200500689

  日期：2005.7.4
• Triple-Decker Complexes Formed via the Weak Link Approach
  作者：You-Moon Jeon、Jungseok Heo、Aaron M. Brown、Chad A. Mirkin

  DOI：10.1021/om0602310

  日期：2006.5.1

  Through the weak link approach and a halide-induced ligand rearrangement process, semi-open and condensed triple-decker complexes (TDCs) were prepared and fully characterized. These triple-decker structures with tailorable layers through choice of hemilabile ligand starting materials can be chemically opened and closed to expose the interior layer in a reversible fashion using small-molecule and elemental anion ligand substitution reactions.
• Novel Hemilabile (Phosphinoalkyl)arene Ligands:  Mechanistic Investigation of an Unusual Intramolecular, Arene−Arene Exchange Reaction
  作者：Elizabeth T. Singewald、Xiaobo Shi、Chad A. Mirkin、Susan J. Schofer、Charlotte L. Stern

  DOI：10.1021/om960114c

  日期：1996.6.25

  The novel, hemilabile (phosphinoalkyl)arene ligands ArX(CH2)(2)PPh(2) (1a, Ar = C6H5, X = O; 1b, Ar = C6H5, X = CH2; 1c, Ar = FC6H4, X = CH2) were synthesized and complexed to Rh(I) to form the bis(phosphine), eta(6)-arene piano stool complexes [(eta(6):eta(1)-ArX(CH2)(2)PPh(2))Rh(eta(1)-ArX(CH2)(2)PPh(2))]BF4 (2a-c). Complexes 2a-c were fully characterized in solution, and complex 2a was characterized by single-crystal X-ray diffraction methods. Two of these complexes, 2a,c, undergo an unusual, degenerate eta(6)-arene, free arene exchange reaction which was studied by 2-D NMR EXSY experiments. A mechanism for the exchange reaction of 2a which involves the formation of a square planar, cis-phosphine, cis-ether Rh(I) complex, [Rh(eta(2)-PhO(CH2)(2)PPh(2))(2)]BF4 (13), is proposed.