1,4-bis(2-diphenylphosphinoethoxy)benzene | 252335-14-1

• 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-diphenylphosphinoethoxy)benzene
• 英文别名: 1,4-(PPh2CH2CH2O)2C6H4；2-[4-(2-Diphenylphosphanylethoxy)phenoxy]ethyl-diphenylphosphane
• CAS: 252335-14-1
• 化学式: C₃₄H₃₂O₂P₂
• 分子量: 534.574
• InChiKey: WINGVIIXRZEYDO-UHFFFAOYSA-N

物化性质

• 沸点：
  661.0±45.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.5
• 重原子数：
  38
• 可旋转键数：
  12
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.12
• 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：

  1,4-bis(2-diphenylphosphinoethoxy)benzene 以 二氯甲烷 、 氘代甲醇 、 丙酮 为溶剂， 生成 [(μ2-(1,4-(PPh2CH2CH2O)2C6H4)2(CN)4Pd2)]
  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

• Binuclear Ruthenium Macrocycles Formed via the Weak-Link Approach
  作者：Meisa S. Khoshbin、Maxim V. Ovchinnikov、Chad A. Mirkin、Lev N. Zakharov、Arnold L. Rheingold

  DOI：10.1021/ic048975y

  日期：2005.2.1

  The "weak-link approach" for the synthesis of metallomacrocycles has been used to synthesize a series of novel Ru(II) macrocycles in high yield. RuCl2(PPh3)3 has been reacted with two different phosphino-alkyl-ether hemilabile ligands, 1,4-(PPh2(CH2)2O)2C6H4 and 1,4-(PPh2(CH2)2OCH2)2C6H4. The hemilabile bidentate ligand coordinates to Ru(II) centers through both the P and O atoms to form bimetallic

  用于合成金属大环化合物的“弱连接方法”已用于以高产率合成一系列新颖的Ru（II）大环化合物。RuCl2（PPh3）3已与两个不同的膦-烷基-醚半不稳定配体1,4-（PPh2（CH2）2O）2C6H4和1,4-（PPh2（ ）2O ）2C6H4反应。半不稳定的双齿配体通过P和O原子配位到Ru（II）中心，形成双金属“缩合中间体”。弱的Ru-O键已被CO，1,2-二氨基丙烷和吡啶选择性地裂解，从而产生大的开放大环。这是用于用Ru合成大环的弱连接方法的第一个示例，一般来说，金属中心具有四个以上的配位点。
• Binuclear Copper(I) Macrocycles Synthesized via the Weak-Link Approach
  作者：Martin S. Masar、Chad A. Mirkin、Charlotte L. Stern、Lev N. Zakharov、Arnold L. Rheingold

  DOI：10.1021/ic049658u

  日期：2004.7.1

  into these macrocycles provides a pathway to complexes that differ from analogous d8 square planar macrocycles generated via this approach in their increased air stability, small molecule reactivity, and ability to form multiple structural isomers. Solid-state structures, as determined by single-crystal X-ray diffraction studies, are presented for condensed intermediates and an open macrocycle

  弱链接方法已被用来以高收率合成一系列双金属Cu（I）大环。将膦烷基烷基醚或-硫醚配体加至[Cu（MeCN）4] PF6会产生“缩合”中间体[mu-（1,4-（PPh2CH2CH2X）2Y）2Cu2] [PF6] 2（X = S，O; Y = C6H4，C6F4），包含强P-Cu键和较弱的O-Cu或S-Cu键。这些中间体的弱键可以通过配体取代反应裂解，生成大环结构[mu-（1,4-（PPh2CH2CH2X）2Y）2（Z）nCu2] [PF6] 2（X = S，O; Y = ， ； Z =吡啶，乙腈，二亚胺，异氰化物）的定量收率基本相同。将四面体Cu（I）金属中心并入这些大环化合物为复合物提供了一条途径，该复合物与通过该方法生成的类似d8方形平面大环化合物在增加的空气稳定性方面有所不同，小分子反应性，以及形成多种结构异构体的能力。通过单晶X射线衍射研究确定的固态结构，用于缩合中间体和开放大环化合物
• 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.