propa-1,2-dienylphosphine | 133672-87-4

• 分子结构分类: 有机化合物 - 有机磷化合物
• 英文名称: propa-1,2-dienylphosphine
• 英文别名: 1,2-propadienylphosphine；propadienylphosphine；allenylphosphine；propa-1,2-dienylphosphane
• CAS: 133672-87-4
• 化学式: C₃H₅P
• 分子量: 72.0465
• InChiKey: WWPYBNWNNHQNDJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.16
• 重原子数：
  4.0
• 可旋转键数：
  0.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  propa-1,2-dienylphosphine 在 diborane(6) 作用下， 以 正戊烷 为溶剂， 以75%的产率得到allenylphosphine-borane
  参考文献：
  名称：

  硼烷络合的动力学不稳定的膦的合成，光电子能谱和量子化学研究。

  摘要：

  乙炔基和烯丙基膦基硼烷是通过在低温下将硼烷加到游离膦上来制备的。通过在真空中选择性捕集来进行纯化，并通过NMR，红外光谱法和质谱法对络合物进行表征。观察到动力学稳定性低于相应的自由体系。通过光电子能谱和B3LYP / aug-cc-pVTZ量子化学研究，研究了由这些化合物以及甲基，乙烯基，烯丙基和炔丙基膦-硼烷组成的系列，以定义自由系统与电子之间的电子效应变化。相应的复合体。尽管络合只会导致不饱和部分发生微小变化，但由于电荷从磷到硼的转移，PC键在所有情况下均会缩短。在络合物和自由体系中可以发现类似的旋转异构体，并且仅在烯丙基衍生物的情况下，相对稳定性的顺序相反。计算的络合能在80-100 kJ mol（-1）之间，与快速真空热解实验一致。在α，β-不饱和化合物的情况下，通过改变游离膦中孤电子对和π键之间的直接共轭到σ（PB）键与不饱和键的超共轭的变化，可以轻松描述光电子光谱相应的复合衍生

  DOI：

  10.1039/b823186a
• 作为产物：
  描述：

  5,5-dimethyl-2-oxo-2-(propa-1',2'-diene)-1,3,2-dioxaphosphorinane 在 dichloroalane 作用下， 以 various solvent(s) 为溶剂， 以77%的产率得到propa-1,2-dienylphosphine
  参考文献：
  名称：

  Structural and Conformational Properties of 1,2-Propadienylphosphine (Allenylphosphine) Studied by Microwave Spectroscopy and Quantum Chemical Calculations

  摘要：

  1,2-Propadienylphosphine (allenylphosphine), H2C=C=CHPH2, has been investigated by Stark and Fourier transform microwave spectroscopy. Two rotameric forms denoted syn and gauche have been assigned. The syn form has a symmetry plane (C-s symmetry) where the lone electron pair of phosphorus points toward the double bonds. The phosphino group is rotated roughly 120degrees from this position in the gauche rotamer. The dipole moment of syn was determined to be mu(a) = 1.613(23), mu(b) = 2.347(24) mu(c) = 0 (for symmetry reasons), and mu(tot) = 2.848(28) x 10(-30) C m [0.854(8) D]. The energy difference between the two forms was found to be 2.1(4) kj/mol from relative intensity measurements with syn as the more stable conformer. Extensive quantum chemical calculations have been carried out and accurate equilibrium structures have been determined for these two rotamers, as well as for the corresponding two conformers of vinylphosphine (H2C=CHPH2).

  DOI：

  10.1021/jp047207p

文献信息

• Guillemin, Jean-Claude; Savignac, Philippe; Denis, Jean-Marc, Inorganic Chemistry, 1991, vol. 30, # 9, p. 2170 - 2173
  作者：Guillemin, Jean-Claude、Savignac, Philippe、Denis, Jean-Marc

  DOI：——

  日期：——
• Structural and Conformational Properties of 1,2-Propadienylphosphine (Allenylphosphine) Studied by Microwave Spectroscopy and Quantum Chemical Calculations
  作者：Harald Møllendal、Jean Demaison、Denis Petitprez、Georges Wlodarczak、Jean-Claude Guillemin

  DOI：10.1021/jp047207p

  日期：2005.1.1

  1,2-Propadienylphosphine (allenylphosphine), H2C=C=CHPH2, has been investigated by Stark and Fourier transform microwave spectroscopy. Two rotameric forms denoted syn and gauche have been assigned. The syn form has a symmetry plane (C-s symmetry) where the lone electron pair of phosphorus points toward the double bonds. The phosphino group is rotated roughly 120degrees from this position in the gauche rotamer. The dipole moment of syn was determined to be mu(a) = 1.613(23), mu(b) = 2.347(24) mu(c) = 0 (for symmetry reasons), and mu(tot) = 2.848(28) x 10(-30) C m [0.854(8) D]. The energy difference between the two forms was found to be 2.1(4) kj/mol from relative intensity measurements with syn as the more stable conformer. Extensive quantum chemical calculations have been carried out and accurate equilibrium structures have been determined for these two rotamers, as well as for the corresponding two conformers of vinylphosphine (H2C=CHPH2).
• Synthesis, photoelectron spectroscopy and quantum chemical study of kinetically unstabilized phosphines complexed by borane
  作者：Balázs Németh、Brahim Khater、Tamás Veszprémi、Jean-Claude Guillemin

  DOI：10.1039/b823186a

  日期：——

  selective trapping in vacuo and the complexes were characterized by NMR and infrared spectroscopy and mass spectrometry. A kinetic stability lower than that of the corresponding free systems was observed. A series composed of these compounds and methyl-, vinyl-, allyl- and propargylphosphine-boranes was investigated by photoelectron spectroscopy and B3LYP/aug-cc-pVTZ quantum chemical study in order to define

  乙炔基和烯丙基膦基硼烷是通过在低温下将硼烷加到游离膦上来制备的。通过在真空中选择性捕集来进行纯化，并通过NMR，红外光谱法和质谱法对络合物进行表征。观察到动力学稳定性低于相应的自由体系。通过光电子能谱和B3LYP / aug-cc-pVTZ量子化学研究，研究了由这些化合物以及甲基，乙烯基，烯丙基和炔丙基膦-硼烷组成的系列，以定义自由系统与电子之间的电子效应变化。相应的复合体。尽管络合只会导致不饱和部分发生微小变化，但由于电荷从磷到硼的转移，PC键在所有情况下均会缩短。在络合物和自由体系中可以发现类似的旋转异构体，并且仅在烯丙基衍生物的情况下，相对稳定性的顺序相反。计算的络合能在80-100 kJ mol（-1）之间，与快速真空热解实验一致。在α，β-不饱和化合物的情况下，通过改变游离膦中孤电子对和π键之间的直接共轭到σ（PB）键与不饱和键的超共轭的变化，可以轻松描述光电子光谱相应的复合衍生