(E,E)-1,3-bis<2-(2,4,6-tri-t-butylphenyl)-2-phosphaethenyl>benzene | 139924-43-9

• 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: (E,E)-1,3-bis<2-(2,4,6-tri-t-butylphenyl)-2-phosphaethenyl>benzene
• 英文别名: (Z,Z)-1,3-bis<2-(2,4,6-tri-t-butylphenyl)-2-phosphaethenyl>benzene；(E,E)-1,3-bis[2-(2,4,6-tri-t-butylphenyl)-2-phosphaethenyl]benzene；(2,4,6-Tritert-butylphenyl)-[[3-[(2,4,6-tritert-butylphenyl)phosphanylidenemethyl]phenyl]methylidene]phosphane
• CAS: 139924-43-9
• 化学式: C₄₄H₆₄P₂
• 分子量: 654.94
• InChiKey: MFWKDGFBNTWASP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.5
• 重原子数：
  46
• 可旋转键数：
  10
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.55
• 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：

  tetrakis(acetonitrile)palladium(II) tetrafluoroborate 、 (E,E)-1,3-bis<2-(2,4,6-tri-t-butylphenyl)-2-phosphaethenyl>benzene 以 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  苯并二磷烯烃配体及其 PdII 和 PtII 配合物：它们的合成、结构和还原产物的 ESR 研究

  摘要：

  合成了新的双磷烯烃 1,3-双[2-(2,4,6-三-叔丁基苯基)膦二甲基]苯。由于存在两个 P=C 键，通过 31 P NMR 观察到三种异构体（EE、EZ、ZZ），并且可以确定其中两种的晶体结构（EE、ZZ）。L 的电化学行为已通过循环伏安法进行了研究：准可逆还原发生在 -1.89 V/SCE，对应于已通过 ESR 在可变温度下研究的自由基阴离子的形成。实验 31P 和 'H 超精细常数与室温下 P=C 和 Cphosphaalkene-C苯键的自由旋转一致，并与 ab initio 预测一致。L 的一种异构体与钯 (I1) 和铂 (I1) 离子形成络合物。晶体结构表明 L 是正金属化的，并通过将金属与每个磷原子配位而充当三齿配体。这些复合物在 -0.92 和 - 1.29 V 之间进行电化学还原，并通过 ESR 在液体和冷冻溶液中研究产生的顺磁性物质。这种还原过程被证明是一个以配体为

  DOI：

  10.1021/ja00113a014
• 作为产物：
  描述：

  (2,4,6-三-叔-丁基苯基)膦 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 生成 (E,E)-1,3-bis<2-(2,4,6-tri-t-butylphenyl)-2-phosphaethenyl>benzene
  参考文献：
  名称：

  Preparation and photoisomerization of 2-phosphaethenylbenzenes having more than one phosphorus=carbon double bond

  摘要：

  Phosphaethenes having more than one phosphorus-carbon double bond on a benzene ring were prepared. The E/Z photoisomerization reactions of these phosphaethenes were studied using P-31 NMR spectroscopy. The structure of 1,2-bis[2-(2,4,6-tri-t-butylphenyl)-2-phosphaethenyl]benzene was determined by X-ray crystallographic analysis. (C) 1997 Elsevier Science S.A.

  DOI：

  10.1016/s0022-328x(96)06939-2

文献信息

• Phosphaalkenes palladium(II) complexes in the suzuki and sonogashira cross-coupling reactions
  作者：Bernard Deschamps、Xavier Le Goff、Louis Ricard、Pascal Le Floch

  DOI：10.1002/hc.20307

  日期：2007.5

  methoxy group. Reaction of two equivalents of ligand 1 with the [Pd(allyl)Cl]2 dimer affords complex 5, in which the two ligands are coordinated through their phosphorus atom. The catalytic activity of complex 5 was compared to that of the 1,3-bis[2-(supermesityl)phosphanediylmethyl]benzene palladium chloride complex (6). Performances of the two catalysts were found to be similar in the Suzuki cross-coupling

  1-甲氧基-2-(supermesitylphosphanylidenemethyl)-苯配体(1) 是通过磷酸-Wittig 试剂[Mes*PPMe3] 与邻甲氧基苯甲醛反应制备的。1 与一当量的 [Pd(allyl)Cl]2 二聚体在 Ag(OTf) 存在下反应得到中性配合物 (4)，其中三氟甲磺酸酯配体与钯原子配位。DFT 计算表明，相对于螯合物种的形成，配合物 4 的形成有利于 22.4 kcal/mol，该螯合物涉及配体通过一个孤对磷原子在悬垂甲氧基的氧上进行配位。两当量的配体 1 与 [Pd(allyl)Cl]2 二聚体反应得到配合物 5，其中两个配体通过它们的磷原子配位。将配合物 5 的催化活性与配合物 1 的催化活性进行比较，3-双[2-(supermesityl)phosphanediylmethyl]苯氯化钯络合物 (6)。在苯硼酸和一些芳基溴化物之间的 Suzuki 交叉偶联反应（TON
• Preparation and Palladium Complex Formation of Several (2-Phosphaethenyl)benzenes
  作者：Hajime Kawanami、Kozo Toyota、Masaaki Yoshifuji

  DOI：10.1246/cl.1996.533

  日期：1996.7

  Phenylphosphaethenes carrying two to four phosphoruscarbon double bonds on a benzene ring were prepared and their palladium complex formations were studied. The palladium complexes reacted with alkyllithium reagents to give the corresponding o-alkylation products.

  研究人员制备了苯环上带有 2 至 4 个磷碳双键的苯基磷杂环丁烷，并研究了它们的钯络合物形成。钯络合物与烷基锂试剂反应生成相应的邻烷基化产物。
• Synthesis, structure and ligand-centred reduction of an orthometallated complex of palladium containing two phosphaalkene groups
  作者：Abdelaziz Jouaiti、Michel Geoffroy、Gustavo Terron、G�arald Bernardinelli

  DOI：10.1039/c39920000155

  日期：——

  A novel ligand containing two phosphaalkene moieties has been synthesized, which forms a palladium(II) complex whose crystal structure has been determined and whose reduction has been shown, by EPR spectroscopy, to take place on the ligand rather than on the metal.

  合成了一种含有两个磷烯部分的新型配体，该配体形成了钯（II）配合物，其晶体结构已确定，并且通过 EPR 光谱表明其还原发生在配体上而不是金属上。
• Phosphinidene Transfer Reactions of the Terminal Phosphinidene Complex Cp2Zr(:PC6H2-2,4,6-t-Bu3)(PMe3)
  作者：Tricia L. Breen、Douglas W. Stephan

  DOI：10.1021/ja00153a013

  日期：1995.12

  The terminal zirconium phosphinidene complex Cp(2)Zr(PR*)(PMe(3)) (R* = C6H2-2,4,6-t-Bu(3)) 2 has been synthesized in high yield, and its reactivity has been investigated. The compound Cp(2)ZrMe(PHR*) 1 is unstable with respect to the loss of methane; in the presence of PMe(3) this reaction yielded 2. Reactions of 2 with benzophenone, benzaldehyde, or isophthalaldehyde produced phosphaalkenes PhCH=PR* 3, Ph(2)C=PR* 4, and 1,3-C6H2(CH=PR*)(2) 5, respectively. PhN=C=PR* 6 resulted from the reaction of 2 with phenyl isothiocyanate while the use of cyclohexanone afforded the enolate Cp(2)Zr(PHR*)(OC6H9) 7. Phosphinidene group transfer also took place in reactions of 2 with the appropriate organic dihalide or epoxide. In this way phosphaalkenes CH2=PR* 8 and CHCl=PR* 9, phosphirane (CH(2)CH(2)PR*) 10, phospholane 1,2-C6H4(CH(2)PR*)(2) 11 and substituted phosphiranes (CH2CH)(CHCH2-PR*) 12, CH2C(CCH(2)PR*) 13, (PhCHCH(Ph)PR*) 15, and trans-(PhCHCH(2)PR*) 16 were synthesized. The use of propylene oxide yielded the enolate Cp(2)Zr(PHR*)(OCH2CH=CH2) 17. Similar reactions of 2 with heavier group 14 dihalides and sulfides furnished Cp(2)Zr(PR*(SiMe(2)Cl))Cl 18, PR*(SiMe(2)Cl)(2) 19, (Me(2)GeCl)(2) PR* 20, (Me(2)GePR*)(2) 21, (t-Bu(2)SnPR*)(2) 22, and (Me(2)SnPR*)(2) 23. Intramolecular phosphinidene transfer occurred in reactions of 2 with benzonitrile and dicyclohexylcarbodiimide, giving Cp(2)Zr(PMe(3))(NC(Ph)(PR*)) 25 and Cp(2)Zr(N(Cy))(2)C=PR* 26, respectively. Crystallographic data are reported for compounds 22, 25b, and 26.
• Mono- and bi-dentate phosphaalkene ligands: structures of their copper(I) chloride complexes
  作者：Abdelaziz Jouaiti、Michel Geoffroy、G�rald Bernardinelli

  DOI：10.1039/dt9940001685

  日期：——

  While the reaction of the monophosphaalkene [(2,4,6-tri-tert-butylphenyl)phosphanediylmethyl]-benzene (L2) with copper(I) chloride ed to a dimeric complex [Cu2Cl2L22(NCMe)2] 1, use of the diphosphaalkene 1,3-bis[(2,4,6-tri-tert-butylphenyl)phosphanediylmethyl]benzene (L1) gave rise to a tetrameric complex [Cu4Cl4L12].3EtOH 2. The crystal structures of the complexes have been determined and indicate that 1 is a centrosymmetric dimer with tetrahedrally co-ordinated copper(I) centres, whereas 2 adopts a 'cubane-like' structure with pairs of copper atoms bridged by different L1 units.