1,4-bis(2-diphenylphosphanylethoxy)-2,3,5,6-tetramethylbenzene | 205743-54-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 1,4-bis(2-diphenylphosphanylethoxy)-2,3,5,6-tetramethylbenzene
• 英文别名: 1,4-(PPh2CH2CH2O)2-2,3,5,6-((CH3)4C6)；1,4-(Ph2PCH2CH2O)2C6Me4；2-[4-(2-Diphenylphosphanylethoxy)-2,3,5,6-tetramethylphenoxy]ethyl-diphenylphosphane
• CAS: 205743-54-0
• 化学式: C₃₈H₄₀O₂P₂
• 分子量: 590.682
• InChiKey: CCFFGJYFWOORBB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9
• 重原子数：
  42
• 可旋转键数：
  12
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  tetrakis(acetonitrile)palladium(II) tetrafluoroborate 、 1,4-bis(2-diphenylphosphanylethoxy)-2,3,5,6-tetramethylbenzene 以 二氯甲烷 、 丙酮 为溶剂， 以93.9%的产率得到[(μ-(1,4-(PPh2CH2CH2O)2-2,3,5,6-(CH3)4C6)2Pd2)][BF4]4*0.5CD3NO2
  参考文献：
  名称：

  通过弱链接方法合成的双核钯大环化合物

  摘要：

  金属大环合成的“弱连接方法”已被用来高产率地合成一系列Pd（II）大环。尽管已使用该方法构建具有多种配体的几种Rh（I）配合物，但尚未证明该方法相对于过渡金属的普遍性。当添加到[Pd（NCCH 3）4 ] [BF 4 ] 2中时，膦烷基烷基醚或硫醚配体产生“缩合中间体”，[（μ-（1,4-（PPh 2 CH 2 CH 2 X）2 -Y ）2 Pd 2）] [BF 4 ] 4（4，X ＝ O，Y ＝ 2,3,5,6-（（CH 3）4 C 6）；5，X ＝ O，Y ＝ C 6 H 4； n ＝1。在图6中，X ＝ S，Y ＝ C 6 H 4），包含强的P-Pd键和较弱的O-Pd或S-Pd键。这些中间体的弱键可以通过简单的配体取代反应定量破坏，以生成大环结构[[μ-（1,4-（PPh 2 CH 2 CH 2 X）2 -Y）2（Z）4 Pd 2） ] [BF 4 ] n（7，X = O，Y = 2

  DOI：

  10.1021/om001042z

文献信息

• Templated Formation of Binuclear Macrocycles via Hemilabile Ligands
  作者：Joshua R. Farrell、Adam H. Eisenberg、Chad A. Mirkin、Ilia A. Guzei、Louise M. Liable-Sands、Christopher D. Incarvito、Arnold L. Rheingold、Charlotte L. Stern

  DOI：10.1021/om990585+

  日期：1999.11.1

  A new approach to synthesizing binuclear metallomacrocycles is reported. This approach utilizes flexible bisphosphine alkyl-aryl ether hemilabile ligands which complex Rh(I) to form "condensed" macrocycles held together by a series of both strong and weak links of the following type: [(kappa(2):mu(2):kappa(2)-(1,4-(Ph2PCH2CH2O)(2)-2,3,5,6-((CH3)(4)C-6)))(2)Rh-2][BF4](2) (5a) or [mu(2),eta(1): eta(6):eta(1)-(1,4-(Ph2P(CH2)(n)O)(2)-X))(2)Rh-2][BF4](2) (5b, n = 2, X = 2,3,5,6-((CH3)(4)C-6); 6, n = 3, X = 2,3,5,6-((CH3)(4)C-6); 7, n = 2, X = C6H4; 8, n = 2, X = C6H4-C6H4) Introduction of ligands that will bind to Rh(I) more strongly than either the Rh-eta(6)-aryl or Rh-eta(1)-ether weak links of 5a-8 results in the breaking of the weak links to form a series of 26-34-membered macrocylic ring structures such as [mu(2)-(1,4-(Ph2P(CH2)(n)O)(2)X))(2)(L-1)(m)(L-2)(o)Rh-2][BF4](2) (9, n = 2, X = 2,3,5,6-((CH3)(4)C-6)), L-1 = CO, m = 6, L-2 = none; 10, n = 2, X = C6H4, L-1 = CO, m = 6, L-2 = none; 11, n = 2, X= C6H4-C6H4; L-1 = CO, m = 6, L-2 = none; 12, n = 2, X = 2,3,5,6-((CH3)(4)C-6)), L-1 = CO, m = 2, L-2 = CH3CN, o = 2; 13, n = 3, X = 2,3,5,6-((CH3)(4)C-6)), L-1 = CO, m = 2, L-2 = CH3CN, o = 2; 14, n = 2, X = C6H4, L-1= CO, m = 2, L-2 = CH3CN, o = 2; 15, n = 2, X = C6H4-C6H4, L-1 = CO, m = 2, L-2 = CH3CN, o = 2). These homobimetallic macrocycles can be used to sequester bifunctional aromatic molecules to form host-guest structures such as [mu(2)-(1,4-(Ph2PCH2CH2O)(2)-2,3,5,6-((CH3)(4)C-6)))(2)(CO)(2)(mu(2)-1,4-(-NC)(2)C6H4)- Rh-2][BF4](2) (16) and [mu(2)-(1,4-(Ph2PCH2CH2O)(2)-2,3,5,6-((CH3)(4)C-6)))(2)(CH3CN)(2)(mu(2)-1,4-(-CN)(2)C6H4)- Rh-2][BF4](2) (17). The synthetic methods described within this article represent a powerful new way of making binuclear macrocycles from flexible ligands in nearly quantitative yields. Moreover, the macrocycles are highly tailorable with respect to cavity size and hydrophobicity and the metals' steric and electronic environments. Solid-state structures as determined by single-crystal X-ray diffraction studies are presented for compounds 5a, 6, 7, 9, 10, 12, and 17.
• 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.
• Strategy for Preparing Molecular Cylinders with Synthetically Programmable Structural Parameters
  作者：Joshua R. Farrell、Chad A. Mirkin、Louise M. Liable-Sands、Arnold L. Rheingold

  DOI：10.1021/ja982688+

  日期：1998.11.1
• Farrell; Mirkin; Guzei, Angewandte Chemie - International Edition in English, 1998, vol. 37, # 4, p. 465 - 467
  作者：Farrell、Mirkin、Guzei、Liable-Sands、Rheingold

  DOI：——

  日期：——