氨基二氟膦 | 25757-74-8

• 分子结构分类: 无机化合物 - 均质非金属化合物 - 其他非金属卤化物
• 中文名称: 氨基二氟膦
• 英文名称: aminodifluorophosphine
• 英文别名: (difluorophosphino)amine；Phosphoramidous difluoride
• CAS: 25757-74-8
• 化学式: F₂H₂NP
• 分子量: 84.9931
• InChiKey: MAZAVXNOOKBYCU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  4
• 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：
  26
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  氨基二氟膦 以 neat (no solvent) 为溶剂， 生成 Phosphorodiamidous fluoride 、 氟化磷(III)
  参考文献：
  名称：

  Infrared and Raman spectra, conformational stability, structural parameters, ab initio calculations and vibrational assignments of aminodifluorophosphine

  摘要：

  Infrared spectra (4000-50 cm(-1)) have been recorded for three isotopomers of aminodifluorophosphine, H2NPF2, (H2NPF2)-N-15 and D2NPF2, of the gases. The Raman spectra of all three molecules were recorded of the liquids. To support the vibrational assignment MP2(full) ab initio calculations with the 6-31G(d) basis set were carried out to predict the fundamental vibrational frequencies, infrared intensities, Raman activities, depolarization values and infrared band contours. Additional ab initio calculations employing a variety of basis sets with and without diffuse functions have been used to predict the conformational stability, structural parameters and centrifugal distortion constants. These predictions are compared to previously reported experimental values when available. The adjusted r(0) structural parameters have been obtained by systematically fitting the MP2(full)/6-311+G(d) predicted values with the previously reported rotational constants for five isotopomers obtained from the microwave study. The difference in the two NH distances is 0.003 angstrom which is much smaller than the value of 0.021 angstrom previously reported. The bonding around the nitrogen atom is effectively planar which is consistent with the previously reported structural information from the microwave study but differs from the reported slightly pyramidal bonding obtained in the electron diffraction investigation. The adjusted r(0) heavy atom distances and angles are: r(PF) = 1.587(3); r(NP) = 1.649(3) angstrom; angle FPF = 94.7(5); angle NPF = 100.6(5)degrees. Vibrational assignments are given for H2NPF2, (H2NPF2)-N-15 and D2NPF2 which are supported by ab initio MP2/6-31G(d) calculations. These results are compared to the corresponding quantities of some similar molecules. (c) 2008 Published by Elsevier B.V.

  DOI：

  10.1016/j.molstruc.2007.04.045
• 作为产物：
  描述：

  chlorodifluorophosphine 、 氨 以 neat (no solvent, gas phase) 为溶剂， 生成 氨基二氟膦
  参考文献：
  名称：

  Infrared and Raman spectra, conformational stability, structural parameters, ab initio calculations and vibrational assignments of aminodifluorophosphine

  摘要：

  Infrared spectra (4000-50 cm(-1)) have been recorded for three isotopomers of aminodifluorophosphine, H2NPF2, (H2NPF2)-N-15 and D2NPF2, of the gases. The Raman spectra of all three molecules were recorded of the liquids. To support the vibrational assignment MP2(full) ab initio calculations with the 6-31G(d) basis set were carried out to predict the fundamental vibrational frequencies, infrared intensities, Raman activities, depolarization values and infrared band contours. Additional ab initio calculations employing a variety of basis sets with and without diffuse functions have been used to predict the conformational stability, structural parameters and centrifugal distortion constants. These predictions are compared to previously reported experimental values when available. The adjusted r(0) structural parameters have been obtained by systematically fitting the MP2(full)/6-311+G(d) predicted values with the previously reported rotational constants for five isotopomers obtained from the microwave study. The difference in the two NH distances is 0.003 angstrom which is much smaller than the value of 0.021 angstrom previously reported. The bonding around the nitrogen atom is effectively planar which is consistent with the previously reported structural information from the microwave study but differs from the reported slightly pyramidal bonding obtained in the electron diffraction investigation. The adjusted r(0) heavy atom distances and angles are: r(PF) = 1.587(3); r(NP) = 1.649(3) angstrom; angle FPF = 94.7(5); angle NPF = 100.6(5)degrees. Vibrational assignments are given for H2NPF2, (H2NPF2)-N-15 and D2NPF2 which are supported by ab initio MP2/6-31G(d) calculations. These results are compared to the corresponding quantities of some similar molecules. (c) 2008 Published by Elsevier B.V.

  DOI：

  10.1016/j.molstruc.2007.04.045
• 作为试剂：
  描述：

  六氟丙酮 在 氨基二氟膦 作用下， 反应 24.0h， 生成 1,1,1,3,3,3-六氟-2-丙亚胺 、 2,2-difluoro-4,4,5,5-tetrakis(trifluoromethyl)-1,3,2λ⁵-dioxaphospholane-2-amine 、 三(六氟异丙基)磷酸酯 、 Difluorophosphorsaeure-<2,2,2-trifluor-1-(trifluormethyl)ethylester> 、 Fluorophosphorsaeure-bis<2,2,2-trifluor-1-(trifluormethyl)ethylester>
  参考文献：
  名称：

  Storzer, Werner; Roeschenthaler, Gerd-Volker; Schmutzler, Reinhard, Chemische Berichte, 1981, vol. 114, # 11, p. 3609 - 3624

  摘要：

  DOI：

文献信息

• Preparation and chemical and spectroscopic properties of (disilylamino)difluorophosphine and bis(difluorophosphino)silylamine
  作者：E. A. V. Ebsworth、David W. H. Rankin、John G. Wright

  DOI：10.1039/dt9790001065

  日期：——

  N(PF2)2(SiH3) have been prepared by the reactions of SiBrH3 and NMe3 with PF2[NH(SiH3)] and NH(PF2)2 respectively. Vibrational, n.m.r., mass, and photoelectron spectra have been recorded, and chemical properties have been studied. With diborane, PF2[N(SiH3)2] gives the adduct PF2[N(SiH3)2]·BH3 and N(PF2)2(SiH3) gives both mono- and bis-(borane) adducts; n.m.r. spectre of the three borane adducts have

  通过SiBrH 3和NMe 3与PF 2 [NH（SiH 3）]和NH（PF 2）的反应制备了化合物PF 2 [N（SiH 3）2 ]和N（PF 2）2（SiH 3）。）2。记录了振动，核磁共振，质量和光电子能谱，并对化学性质进行了研究。与乙硼烷一起，PF 2 [N（SiH 3）2 ]生成加合物PF 2 [N（SiH 3）2 ]·BH 3和N（PF 2）2（SiH 3）生成单-和双-（硼烷）加合物；记录了三种硼烷加合物的核磁共振谱。在与HBr的反应中，PN键优先受到攻击，而在与水的反应中，Si-N键的裂解首先发生。
• Preparation and properties of diaminodifluorophosphorane
  作者：David E. J. Arnold、David W. H. Rankin

  DOI：10.1039/dt9760001130

  日期：——

  Diaminodifluorophosphorane, PF2H(NH2)2, has been prepared by the reaction of chlorodifluorophosphine and ammonia, and has been characterised spectroscopically. Its vibrational spectra can be interpreted in terms of C2ν symmetry, with a trigonal-bipyramidal structure with axial fluorine atoms. N.m.r. spectra are consistent with this structure, and show that the amino-groups rotate rapidly at room temperature

  通过氯二氟膦与氨的反应制备了二氨基二氟磷烷PF 2 H（NH 2）2，并进行了光谱表征。其振动光谱可以在C来解释2 ν对称，具有三角-双锥结构具有轴向氟原子。Nmr光谱与此结构一致，表明氨基在室温下快速旋转，但在冷却时变慢。报告了偶合常数PF 2 H（15 NH 2）2的符号和大小。
• Preparation and chemical and spectroscopic properties of bis(difluorophosphino) selenide
  作者：David E. J. Arnold、Ernest R. Cromie、David W. H. Rankin

  DOI：10.1039/dt9770001999

  日期：——

  Bis(difluorophosphino) selenide has been prepared by the exchange reactions of PBrF2 and PCLF2 with Se(SiH3)2 and Se(SnBu3)2. It has been characterised by vrbrational, mass, n.m.r., and photoelectron spectroscopy. Spectroscopic results have also been obtained for bis(difluorophosphino) sulphide, prepared by analogous methods. Both compounds react with Brønsted acids to give PF2HSe or PF2HS, and a difluorophos-phine

  通过PBrF 2和PCLF 2与Se（SiH 3）2和Se（SnBu 3）2的交换反应制备了双（二氟膦基）硒化物。它的特征是可变光谱，质谱，核磁共振和光电子能谱。通过类似方法制备的双（二氟膦基）硫化物也获得了光谱结果。两种化合物均与布朗斯台德酸反应生成PF 2 HSe或PF 2 HS，以及该酸的二氟膦衍生物。通过与乙硼烷反应生成单硼烷加合物，以及从[Mo（C 7 H 8）（CO）4 ]。后一反应说明了这些化合物作为螯合双齿配体的潜在用途。与氯一起，硒化物产生PCl 3 F 2和PClF 2 Se。
• Preparation and spectroscopic properties of amines containing germyl and difluorophosphino-groups
  作者：E. A. V. Ebsworth、David W. H. Rankin、John G. Wright

  DOI：10.1039/dt9770002348

  日期：——

  been prepared from the appropriate primary and secondary difluorophosphinoamines by reaction with germyl halide and trimethylamine. The compounds are all much more stable than trigermylamine, but decompose at room temperature by elimination of GeH2. Vibrational, photoelectron, n.m.r., and mass spectroscopic data have been recorded, and are interpreted in terms of the probable conformations adopted by

  化合物PF 2 [NH（GeH 3）]，PF 2 [N（GeH 3）2 ]，PF 2 [N（GeH 3）（SiH 3）]和N（GeH 3）（PF 2）2已经为由适当的伯和仲二氟膦胺与germ酰卤和三甲胺反应制得。这些化合物都比三germylamine稳定得多，但在室温下通过消除GeH 2分解。记录了振动，光电子，核磁共振和质谱数据，并根据氟膦基所采用的可能构象进行了解释。
• Gas-phase molecular structure of bis(difluorophosphino)amine, determined by electron diffraction
  作者：Christopher M. Huntley、Graham S. Laurenson、David W. H. Rankin

  DOI：10.1039/dt9800000954

  日期：——

  The molecular geometry of bis(difluorophosphino)amine, NH(PF2)2, in the gas phase has been studied by electron diffraction. Principal parameters are: ra(P–F) 158.4(3), ra(P–N) 168.4(8) pm; FPF 95.6(10), FPN 98.3(7), and PN P 122.1(7)°. Two conformers are present in the vapour at room temperature. The predominant form (72%) has almost C2v symmetry, but the PF2 groups are twisted 5°away from most symmetrical

  通过电子衍射研究了气相中双（二氟膦基）胺NH（PF 2）2的分子几何结构。主要参数为：r a（PF）158.4（3），r a（PF）168.4（8）pm；FPF 95.6（10），FPN 98.3（7）和PN P 122.1（7）°。在室温下，蒸气中存在两个构象异构体。主要形式（72％）几乎具有C 2 v对称性，但PF 2基团与大多数对称位置相距5°。在一种较不丰富的形式中，一个PF 2基团从C 2 v位置扭曲60°，而另一个仅扭曲5°。

表征谱图