P,P-di-4-morpholinyl-N-phenylphosphinic amide | 65620-43-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 恶嗪烷类
• 英文名称: P,P-di-4-morpholinyl-N-phenylphosphinic amide
• 英文别名: N-phenyl-N',N''-bis(morpholinyl)phosphoric triamide；PhNHP(O)(NC4H8O)2；P(O)(PhNH)(NC4H8O)2；N-dimorpholin-4-ylphosphorylaniline
• CAS: 65620-43-1
• 化学式: C₁₄H₂₂N₃O₃P
• 分子量: 311.321
• InChiKey: JGTOIYXKCXFEBX-UHFFFAOYSA-N

物化性质

• 熔点：
  192 °C(Solv: methanol (67-56-1))
• 沸点：
  455.4±55.0 °C(Predicted)
• 密度：
  1.28±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  54
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  P,P-di-4-morpholinyl-N-phenylphosphinic amide 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 48.0h， 生成
  参考文献：
  名称：

  钯和镍催化的乙烯聚合和与极性单体共聚的多功能PNPO配体

  摘要：

  不对称的PO型配体是钯和镍催化的乙烯聚合以及乙烯与极性单体共聚的通用平台。在这项工作中，制备了一系列膦胺氨基磷酸酯/磷酰胺配体和相应的钯/镍催化剂，在乙烯聚合以及乙烯与各种极性单体的共聚中进行了表征和研究。钯和镍配合物在乙烯（共）聚合反应中表现出高活性，生成高分子量聚乙烯以及乙烯与极性单体的共聚物。在钯催化体系中引入给电子性取代基可以显着增加聚合物分子量，同时保持较高的乙烯（共）聚合活性。镍催化剂中电子给体较少的取代基导致乙烯聚合和与极性单体共聚的催化活性增加。这些结果证明了在乙烯聚合和共聚反应中调节镍和钯催化剂性能的配体电子效应的重要性。

  DOI：

  10.1016/j.jcat.2020.11.023
• 作为产物：
  描述：

  吗啉 、 苯胺 在 三氯氧磷 作用下， 生成 P,P-di-4-morpholinyl-N-phenylphosphinic amide
  参考文献：
  名称：

  钯和镍催化的乙烯聚合和与极性单体共聚的多功能PNPO配体

  摘要：

  不对称的PO型配体是钯和镍催化的乙烯聚合以及乙烯与极性单体共聚的通用平台。在这项工作中，制备了一系列膦胺氨基磷酸酯/磷酰胺配体和相应的钯/镍催化剂，在乙烯聚合以及乙烯与各种极性单体的共聚中进行了表征和研究。钯和镍配合物在乙烯（共）聚合反应中表现出高活性，生成高分子量聚乙烯以及乙烯与极性单体的共聚物。在钯催化体系中引入给电子性取代基可以显着增加聚合物分子量，同时保持较高的乙烯（共）聚合活性。镍催化剂中电子给体较少的取代基导致乙烯聚合和与极性单体共聚的催化活性增加。这些结果证明了在乙烯聚合和共聚反应中调节镍和钯催化剂性能的配体电子效应的重要性。

  DOI：

  10.1016/j.jcat.2020.11.023

文献信息

• Structure, bonding, electronic and energy aspects of a new family of early lanthanide (La, Ce and Nd) complexes with phosphoric triamides: Insights from experimental and DFT studies
  作者：Khodayar Gholivand、Hamid R. Mahzouni、Mehdi D. Esrafili

  DOI：10.1039/c1dt11084e

  日期：——

  A new family of isostructural early lanthanide(III) complexes (LnXPA) of the general formula Ln(XPA)2Cl3(solv)2, where Ln = La, Ce and Nd, XPA = (4-X-C6H4NH)P(O)(NC4H8O)2, X = H, F, Cl and Br, and solv = H2O and CH3OH, is introduced. X-ray crystallography shows that the replacement of the coordinated water by a methanol molecule may reduce the symmetry level of the unit cell from the orthorhombic crystal system and the space groupFdd2 to monoclinic and C2/c. DFT calculations, at B3LYP, PBE and B3PW91 levels, have been carried out to get a better insight into the structural, electronic and energy aspects of the compounds. The large cation attraction energy (−ΔE) values in the range 269–273 kcal mol−1, at the B3PW91/ECP/6-311+G** level for the model complexes XPA–La3+ with stoichiometry 1 : 1, represent new ligands XPA as efficient complexant agents for lanthanides. The electronic nature of para substituent X has no significant effect on the Ln–ligand bonding and cation affinity of the ligands XPA. The results of atoms in molecules (AIM) analysis reveal a partial covalent contribution of the Ln–ligand interaction for the models XPA–La3+ in the absence of counterions and coordinated solvents. In the real complexes LnXPA, a closed-shell Ln–ligand interaction is established. Increasing the charge difference between nitrogen and phosphorus atoms (by ∼0.06 e) associated with a weakening of the Lp(OP)→σ*(P–N) electronic delocalization (Lp(OP) being the lone pair of the phosphoryl oxygen atom) may lead to an increase in partial multiple bond character of the P–N bonds in coordinated ligands, agreeing with the increase in ν(P–N) and 2JPH coupling constant values. The changes in electron density (ρ) and electronic energy density (H(r)) values confirm these structural reorganizations upon complexation.

  在B3PW91/ECP/6-311+G**水平下，模型复合物XPA-La3+的化学计量比为1：1，其大阳离子吸引能（-ΔE）值在269-273千卡/摩尔-1的范围内，表明新配体XPA是镧系元素的有效络合剂。对映取代基X的电子性质对Ln-配体键合和配体XPA的阳离子亲和力没有显著影响。分子中原子（AIM）分析的结果表明，在没有反离子和配位溶剂的情况下，模型XPA-La3+的Ln-配体相互作用具有部分共价性质。在真实的复合物LnXPA中，建立了封闭壳Ln-配体相互作用。增加氮原子和磷原子之间的电荷差（约0.06e），伴随着Lp(OP)→σ*(P-N)电子非局域化（Lp(OP)是磷酰氧原子的孤对）的减弱，可能会导致配位配体中P-N键的部分多重键特征增加，这与在B3PW91/ECP/6-311+G**水平下，模型复合物XPA-La3+的化学计量比为1：1，其大阳离子吸引能（-ΔE）值在269
• High-coordinated lanthanum(III) complexes with new mono- and bidentate phosphoryl donors; spectroscopic and structural aspects
  作者：Khodayar Gholivand、Hamid Reza Mahzouni、Mehrdad Pourayoubi、Shadi Amiri

  DOI：10.1016/j.ica.2010.03.064

  日期：2010.6

  Monodentate and bidentate ligands PhNHP(O)(NC4H8O)(2) (1) and PhC(O) NHP(O)(NH(tert-C4H9))(2) (2) were used to prepare new 7, 9 and 10-coordinated lanthanum(III) complexes; La(1)(2)Cl-3(H2O)(2) (3), La(1)(2)(NO3))(3)H2O center dot La(1)(2)(NO3)(3)CH3CN (4) and La(2)(2)(NO3)(3) (5), respectively. Crystallization of compound 2 in CH3OH:CH3CN leads to one conformer in contrast to the crystallization result from CHCl3:n-C7H16 (two conformers). Compound 4 contains two independent nine-coordinated La(III) complexes that are different in the solvated molecules (H2O and CH3CN). Some structural and electronic perturbations in coordinated ligand were occurred upon complexation, that are confirmed by increase of (2)J(PH), (3)J(PH) and (6)J(PH) coupling constants from the free ligand 1 to complexes 3 and 4. The steric repulsions in the first coordination sphere of La3+ ion, metal-ligand (M-L) binding strength and P=O stretching frequency are very influenced by changing the counter ion from Cl- to NO3-. Comparing the X-ray crystallography data of free ligand 2 with bis-chelated complex 5, it is found that the phosphoryl group is more reactive than carbonyl counterpart. A blue shift of the m(N-H) vibration is observed in line with the weakening of the hydrogen bond from N-H center dot center dot center dot O Phosphoryl in 1 to N-H center dot center dot center dot Cl in 3. Three dimensional butterfly-shape structures are seen in the unit cell of complex 3, which are produced by O-Water-H center dot center dot center dot O-Morpholine hydrogen bonds. (C) 2010 Elsevier B. V. All rights reserved.