phosphine oxide | 13840-40-9

• 分子结构分类: 无机化合物 - 均质非金属化合物 - 其他非金属有机物
• 英文名称: phosphine oxide
• 英文别名: phosphane oxide；Oxidophosphanium
• CAS: 13840-40-9
• 化学式: H₃OP
• 分子量: 49.997
• InChiKey: MPQXHAGKBWFSNV-UHFFFAOYSA-N

物化性质

• 密度：
  1.5735 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  -0.7
• 重原子数：
  2
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  23.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  phosphine oxide 以 水 为溶剂， 生成 次磷酸 、 phosphan
  参考文献：
  名称：

  钌配合物在溶液中生成和捕集氧化膦的实验证据

  摘要：

  从白磷开始，通过电化学方法在溶液中获得了氧化态-1的第一个定义为磷的化合物-氧化膦（H 3 PO）（参见图片）。H 3 PO通过NMR溶液光谱法表征为游离分子，并在互变异构化为亚膦酸H 2 P（OH）后分离为钌（II）配合物中的配体。

  DOI：

  10.1002/anie.201100822
• 作为产物：
  描述：

  氢气 、 二氧化碳 、 phosphan 以 neat (no solvent, gas phase) 为溶剂， 生成 phosphine oxide
  参考文献：
  名称：

  Microwave spectroscopic detection of a transient phosphorus-bearing molecule, H3PO

  摘要：

  The microwave spectrum of the transient phosphine oxide, H3PO, was detected in the gas phase for the first time using a source-modulated spectrometer. The H3PO molecule was generated in a free space cell by a dc glow discharge of a mixture of PH3, CO2, and H2 gases and the corresponding spectral lines for each rotational transition of H3PO formed a pattern clearly indicative of a symmetric top molecule. Isotopomers of H3PO, i.e., H3P18O and D3PO were also produced; H3P18O in the same fashion as for H3PO, and D3PO, in a mixture of D2 and CO2 gases passing over red phosphorus grains. In total, 54 spectral lines of H3PO, 55 lines of H3P18O, and 61 lines of D3PO were measured for the fine structure of rotational transitions, J=2–1 to 12–11. The rotational constant, B0, and centrifugal constants, DJ, DJK, and HKJ were ascertained by a least squares analysis of the measured frequencies for each of the species. Using the rotational constants of the three isotopic species, the following r0 structure was determined: r0 (PO)=1.4763 Å, r0(PH)=1.4406 Å, and ∠HPO=114.26°. The value of each structural parameter deviates significantly from the most recent results predicted by ab initio calculations.

  DOI：

  10.1063/1.478058

文献信息

• Electrochemical generation of P4 2– dianion from white phosphorus
  作者：D. G. Yakhvarov、E. V. Gorbachuk、Kh. R. Khayarov、V. I. Morozov、I. Kh. Rizvanov、O. G. Sinyashin

  DOI：10.1007/s11172-014-0757-6

  日期：2014.11

  Electrochemical reduction of elemental (white) phosphorus in an undivided cell equipped with a sacrificial metal anode (Al, Co, Nb, Sn) results in the formation of the reduced form of white phosphorus, P42– dianion, which was detected in solution by 31P NMR spectroscopy.

  在配备有牺牲金属阳极（Al、Co、Nb、Sn）的未分隔电解槽中，元素（白）磷的电化学还原导致形成还原形式的白磷 P42-二价阴离子，在溶液中由 31P 检测到核磁共振光谱。
• Effect of a sacrificial anode material on the electrochemical generation of phosphane oxide (H3PO)
  作者：Elena V. Gorbachuk、Khasan R. Khayarov、Oleg G. Sinyashin、Dmitry G. Yakhvarov

  DOI：10.1016/j.mencom.2014.11.005

  日期：2014.11

  The highest yields of phosphane oxide in the title process were obtained in electrochemical cells supplied with aluminium (49%), tin (36%) or zinc (67%) anodes.
• Experimental Evidence of Phosphine Oxide Generation in Solution and Trapping by Ruthenium Complexes
  作者：Dmitry Yakhvarov、Maria Caporali、Luca Gonsalvi、Shamil Latypov、Vincenzo Mirabello、Ildar Rizvanov、Oleg Sinyashin、Piero Stoppioni、Maurizio Peruzzini

  DOI：10.1002/anie.201100822

  日期：2011.5.27

  Phosphine oxide (H3PO), the first defined compound of phosphorus in the oxidation state −1, was obtained in solution by electrochemical methods starting from white phosphorus (see picture). H3PO was characterized by NMR solution spectroscopy as a free molecule and isolated as a ligand in ruthenium(II) complexes following tautomerization to phosphinous acid, H2P(OH).

  从白磷开始，通过电化学方法在溶液中获得了氧化态-1的第一个定义为磷的化合物-氧化膦（H 3 PO）（参见图片）。H 3 PO通过NMR溶液光谱法表征为游离分子，并在互变异构化为亚膦酸H 2 P（OH）后分离为钌（II）配合物中的配体。
• Microwave spectroscopic detection of a transient phosphorus-bearing molecule, H3PO
  作者：Imtiaz K. Ahmad、Hiroyuki Ozeki、Shuji Saito

  DOI：10.1063/1.478058

  日期：1999.1.8

  The microwave spectrum of the transient phosphine oxide, H3PO, was detected in the gas phase for the first time using a source-modulated spectrometer. The H3PO molecule was generated in a free space cell by a dc glow discharge of a mixture of PH3, CO2, and H2 gases and the corresponding spectral lines for each rotational transition of H3PO formed a pattern clearly indicative of a symmetric top molecule. Isotopomers of H3PO, i.e., H3P18O and D3PO were also produced; H3P18O in the same fashion as for H3PO, and D3PO, in a mixture of D2 and CO2 gases passing over red phosphorus grains. In total, 54 spectral lines of H3PO, 55 lines of H3P18O, and 61 lines of D3PO were measured for the fine structure of rotational transitions, J=2–1 to 12–11. The rotational constant, B0, and centrifugal constants, DJ, DJK, and HKJ were ascertained by a least squares analysis of the measured frequencies for each of the species. Using the rotational constants of the three isotopic species, the following r0 structure was determined: r0 (PO)=1.4763 Å, r0(PH)=1.4406 Å, and ∠HPO=114.26°. The value of each structural parameter deviates significantly from the most recent results predicted by ab initio calculations.