(1,2-phenylenebis(ethyne-2,1-diyl))bis(diphenylphosphine oxide) | 1426223-00-8

• 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: (1,2-phenylenebis(ethyne-2,1-diyl))bis(diphenylphosphine oxide)
• 英文别名: 1,2-bis(diphenylphosphorylethynyl)benzene；1,2-bis(2-diphenylphosphorylethynyl)benzene
• CAS: 1426223-00-8
• 化学式: C₃₄H₂₄O₂P₂
• 分子量: 526.511
• InChiKey: QFKUNYRQSFUGOM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.4
• 重原子数：
  38
• 可旋转键数：
  6
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1,2-phenylenebis(ethyne-2,1-diyl))bis(diphenylphosphine oxide) 、 [Eu(hfa)₃(H₂O)₂] 以 甲醇 为溶剂， 反应 2.0h， 以26%的产率得到[Eu(hfa)₃(o-dpeb)]₂
  参考文献：
  名称：

  Luminescent Coordination Glass: Remarkable Morphological Strategy for Assembled Eu(III) Complexes

  摘要：

  Syntheses of novel luminescent Eu(III) coordination glasses 1 ([Eu(hfa)(3)(o-dpeb)](2)), 2 ([Eu(hfa)(3)(m-dpeb)](3)), and 3 ([Eu(hfa)(3)(p-dpeb)](n)) are reported. They are composed of Eu(III) ions, hexafluoroacetylacetonato (hfa) ligands, and unique bent-angled phosphine oxide (o-, m-, p-dpeb) ligands with ethynyl groups. Their coordination structures and glass formability are dependent on the regiochemistry of substitution in regard to the internal benzene core. Single-crystal X-ray analyses and DFT calculation reveals dinuclear, trinuclear, and polymer structures for Eu(III) coordination glasses 1, 2, and 3, respectively. Those compounds show characteristic glass-transition (T-g = 25-96 degrees C) and strong luminescence properties (phi(Ln) = 72-94%).

  DOI：

  10.1021/acs.inorgchem.5b00145
• 作为产物：
  描述：

  1,2-diethynylbenzene 在 正丁基锂 、 双氧水 作用下， 以 乙醚 、 二氯甲烷 、 水 为溶剂， 反应 19.0h， 生成 (1,2-phenylenebis(ethyne-2,1-diyl))bis(diphenylphosphine oxide)
  参考文献：
  名称：

  Luminescent Coordination Glass: Remarkable Morphological Strategy for Assembled Eu(III) Complexes

  摘要：

  Syntheses of novel luminescent Eu(III) coordination glasses 1 ([Eu(hfa)(3)(o-dpeb)](2)), 2 ([Eu(hfa)(3)(m-dpeb)](3)), and 3 ([Eu(hfa)(3)(p-dpeb)](n)) are reported. They are composed of Eu(III) ions, hexafluoroacetylacetonato (hfa) ligands, and unique bent-angled phosphine oxide (o-, m-, p-dpeb) ligands with ethynyl groups. Their coordination structures and glass formability are dependent on the regiochemistry of substitution in regard to the internal benzene core. Single-crystal X-ray analyses and DFT calculation reveals dinuclear, trinuclear, and polymer structures for Eu(III) coordination glasses 1, 2, and 3, respectively. Those compounds show characteristic glass-transition (T-g = 25-96 degrees C) and strong luminescence properties (phi(Ln) = 72-94%).

  DOI：

  10.1021/acs.inorgchem.5b00145

文献信息

• Utilizing Redox-Mediated Bergman Cyclization toward the Development of Dual-Action Metalloenediyne Therapeutics
  作者：Sarah E. Lindahl、Hyunsoo Park、Maren Pink、Jeffrey M. Zaleski

  DOI：10.1021/ja308190q

  日期：2013.3.13

  cis-Bergman-cyclized, diiodo product 3 ((31)P: δ = 41 ppm, J(Pt-P) = 3346 Hz) with concomitant loss of 1 equiv of uncyclized phosphine chelate ((31)P: δ = -33 ppm). In contrast, addition of 2 equiv of I2 in the absence of additional radical trap instantaneously forms a metastable Pt(dppeb)2(2+) intermediate species, 4, that is characterized by δ = 51 ppm in the (31)P NMR (J(Pt-P) = 3171 Hz) and ν(C≡C) = 2169

  2 当量的 1,2-双（（二苯基膦基）乙炔基）苯 (dppeb, 1) 与 Pt(cod)Cl2 反应，然后用 N2H4 处理产生还原的 Pt(0) 金属二炔，Pt(dppeb)2, 2。由于接近理想化的四面体几何形状，该配合物在环境条件下对空气氧化和金属介导的伯格曼环化都是稳定的。在过量 1,4-环己二烯 (1,4-CHD) 自由基陷阱存在下，2 与 1 当量的 I2 反应快速且近乎定量地生成顺式伯格曼环化的二碘产物 3 ((31)P: δ = 41 ppm，J(Pt-P) = 3346 Hz)，同时损失 1 当量的未环化膦螯合物（(31)P：δ = -33 ppm）。相比之下，在没有额外自由基陷阱的情况下添加 2 当量的 I2 会立即形成亚稳态 Pt(dppeb)2(2+) 中间物种，4，在(31)P NMR (J(Pt-P) = 3171 Hz) 和 ν(C≡C) = 2169 cm(-1)