4,4'-bis(diphenylphosphoryl)diphenyl ether | 10211-99-1

• 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: 4,4'-bis(diphenylphosphoryl)diphenyl ether
• 英文别名: bis(diphenylphosphoryl)diphenyl ether；dppdO2；1-Diphenylphosphoryl-4-(4-diphenylphosphorylphenoxy)benzene
• CAS: 10211-99-1
• 化学式: C₃₆H₂₈O₃P₂
• 分子量: 570.564
• InChiKey: KPRVUZUYFHCUOG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.7
• 重原子数：
  41
• 可旋转键数：
  8
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4,4'-bis(diphenylphosphoryl)diphenyl ether 、 di(rhodium)tetracarbonyl dichloride 在 正己烷 作用下， 以 甲苯 为溶剂， 以80%的产率得到
  参考文献：
  名称：

  Hydroformylation of styrene and 1-octene catalyzed by binuclear and oligomer rhodium(I) complexes containing the bis-p-phosphinito ligands [(p-Ph2POC6H4)2X] (X=O, CMe2, S)

  摘要：

  The reactions of rhodium(I) substrates with the ligands [(p-Ph2POC6H4)(2)X] (X = O, 1; X = CMe2, 2; X = S, 3) have been studied with the aim to obtain rhodium(I) complexes to utilize as precatalysts in hydroformylation of olefins. The reactions of [Rh(CO)(2)Cl](2) with ligands 1-3, in a Rh to ligand 1:1 molar ratio, in toluene, at room temperature afford the products [Rh(CO)(Cl)(mu-L)](2) (L = 1-3). The reactions of [Rh(acac)(CO)(2)] with 2 are strongly dependent on the ligand nature and experimental conditions. The product formed in a 1:0.5 Rh to ligand molar ratio is dimer with the metal centers held together by the ligand, while the product formed in a 1:1 molar ratio is oligomer. The in situ catalytic systems formed either by [Rh(CO)(2)Cl](2) and ligands 1-3 or by [Rh(acac)(CO)(2)] and 2, at variable ligand-to-metal molar ratio, have been employed in the hydroformylation of styrene and 1-octene. Almost quantitative conversion of styrene was achieved with the catalytic system formed by [Rh(acac)(CO)(2)] and 2, in a 1:0.5 molar ratio, operating at 60 degrees C and 40 atm. The chemoselectivity of the reaction was very high being the linear (L) and the branched (B) aldehydes about 99.9% of the reaction products. The terminal aliphatic olefin 1-octene was hydroformylated with lower conversion in the aldehydes with respect to styrene and isomerization and hydrogenation of the double bond occurred in great extent. Lowering the temperature, the conversion of 1-octene increases but the chemoselectivity drastically decreases owing to the formation of more isomerizarion products, The results have been explained considering both the flexibility and the number of phosphorus atoms (considering each of them as a monodentate ligand) coordinated to each metal center in the trigonal bipyramidal hydridorhodium intermediates formed, namely {[Rh(H)(CO)(3)](2)(mu-2)} (1:0.5 [Rh(acac)(CO)(2)] to 2 molar ratio) and the oligomer [Rh(H)(CO)(2)(mu-2)](n) (1:1 [Rh(acac)(CO)(2)] to 2 molar ratio). In the presence of an excess of ligand 2 the conversion in the aldehydes drastically decreases owing to the rigidity of the intermediate hydridorhodium oligomer species formed. (C) 1999 Published by Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s1381-1169(99)00118-1
• 作为产物：
  描述：

  bis(2-(diphenylphosphanyl )phenyl) ether 在 双氧水 作用下， 以 四氢呋喃 为溶剂， 生成 4,4'-bis(diphenylphosphoryl)diphenyl ether
  参考文献：
  名称：

  大型二氧化二膦配体镧系元素配合物的合成与结构

  摘要：

  摘要三个大位二氧化二膦配体与镧系元素盐反应生成分子或聚合物配合物。这两个柔性配体给出了通式为[Ln（dppfO 2）2 Cl x（NO 3）2-x] [FeCl 4]和[Ln（dppdO 2）2（NO 3）2] NO 3的双螯合物，其中dppfO 2和dppdO 2分别是双（二苯基磷酰基）二茂铁和双（二苯基磷酰基）二苯醚。刚性双（二苯基磷酰基）苯（dppbO 2）与镧系元素盐的反应产生金属与配体化学计量比为1：1.5的线性配位聚合物。通过单晶X射线衍射，IR光谱，质谱和TG / DSC技术研究了这些化合物。

  DOI：

  10.1016/j.poly.2011.03.027

文献信息

• Extremely condensing triplet states of DPEPO-type hosts through constitutional isomerization for high-efficiency deep-blue thermally activated delayed fluorescence diodes
  作者：Jing Zhang、Dongxue Ding、Ying Wei、Hui Xu

  DOI：10.1039/c5sc04848f

  日期：——

  mobility comparable to 44′DPEPO for charge flux balance. Significantly, by virtue of the predominant orientation effect of ortho-DPPO on the T1 location, its T1 state is extremely condensed onto a single phenyl, protected from intermolecular interactions by its remaining five phenyls at its maximum extent. Consequently, 24′DPEPO endowed its DMAC-DPS-based deep-blue devices with state-of-the-art performance

  热激活延迟荧光 (TADF) 染料及其主体作为纯有机分子的相似性使得主体在分子间相互作用中占主导地位，并且对于 TADF 二极管中的激子收集和利用至关重要。DPEPO是最受欢迎的高能隙蓝色 TADF 主体，具有空间位阻邻位取代的二苯基氧化膦 (DPPO) 基团，用于抑制分子间相互作用，但由于其电活性较弱，效率下降严重。相反，对位取代的DPPO具有较小的空间位阻，在分子内电子耦合方面具有优势。在这项工作中，DPEPO的四种结构异构体被构建为二苯醚（DPE) 具有两个在 2 位或 4 位取代的二苯基氧化膦 (DPPO) 基团，即22'DPEPO (即DPEPO )、24DPEPO、24'DPEPO和44'DPEPO。在分离构型的基础上，邻位和对位取代的DPPOs的空间效应和电活性成功地整合到24'DPEPO中，同时由于其不对称构型，分子间相互作用显着降低。与其同类物相比，24'DPEPO具有类