iPr2NC(H)=N-PiPr2 | 1123554-21-1

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: iPr2NC(H)=N-PiPr2
• 英文别名: N'-di(propan-2-yl)phosphanyl-N,N-di(propan-2-yl)methanimidamide
• CAS: 1123554-21-1
• 化学式: C₁₃H₂₉N₂P
• 分子量: 244.36
• InChiKey: ITLJAYBNTMZEKC-NTEUORMPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  15.6
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  iPr2NC(H)=N-PiPr2 在 盐酸 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 以75%的产率得到[iPr2NC(H)=N-P(H)iPr2]Cl
  参考文献：
  名称：

  N ‐Phosphanylformamidines (phosfam) R ₂ ′N–C(H)=N–PR ₂ : One‐Pot Synthesis and Versatile Protonation Reaction

  摘要：

  AbstractA straightforward synthesis of unprecedented N‐phosphanylformamidines (phosfam), 3a,b has been developed. The single‐crystal X‐ray study of 3a revealed an E‐formamidine stereoisomer. The structural parameters show a strong localization of the C1–N1 double bond in the formamidine pattern. Versatile protonation reactions with HCl on 3a and 3b are reported, leading to P–N cleavage vs. prototropy. Experimental studies and DFT calculations have evidenced that the imino nitrogen atom is the basic center of phosfams 3a and 3b. DFT calculations show that the isomers and rotamers of the N‐ and P‐protonated forms of 8a/9a and 8b/9b are energetically close, which prevents conclusions being drawn on the existence of thermodynamic and/or kinetic products. The accessibility of the anti bonding PN orbital (σ*P1N1) is partly responsible for the cleavage of the PN bond in 8a; 8b possesses a less energetically accessible σ*P1N1 orbital which is consistent with the preservation of the PN bond and the quantitative formation of the corresponding phosphonium compound 9b·Cl.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

  DOI：

  10.1002/ejic.200701299
• 作为产物：
  描述：

  二异丙基氨腈 、 氯二异丙基膦 在 [Cp₂Zr(H)Cl]n 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以85%的产率得到iPr2NC(H)=N-PiPr2
  参考文献：
  名称：

  N ‐Phosphanylformamidines (phosfam) R ₂ ′N–C(H)=N–PR ₂ : One‐Pot Synthesis and Versatile Protonation Reaction

  摘要：

  AbstractA straightforward synthesis of unprecedented N‐phosphanylformamidines (phosfam), 3a,b has been developed. The single‐crystal X‐ray study of 3a revealed an E‐formamidine stereoisomer. The structural parameters show a strong localization of the C1–N1 double bond in the formamidine pattern. Versatile protonation reactions with HCl on 3a and 3b are reported, leading to P–N cleavage vs. prototropy. Experimental studies and DFT calculations have evidenced that the imino nitrogen atom is the basic center of phosfams 3a and 3b. DFT calculations show that the isomers and rotamers of the N‐ and P‐protonated forms of 8a/9a and 8b/9b are energetically close, which prevents conclusions being drawn on the existence of thermodynamic and/or kinetic products. The accessibility of the anti bonding PN orbital (σ*P1N1) is partly responsible for the cleavage of the PN bond in 8a; 8b possesses a less energetically accessible σ*P1N1 orbital which is consistent with the preservation of the PN bond and the quantitative formation of the corresponding phosphonium compound 9b·Cl.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

  DOI：

  10.1002/ejic.200701299

文献信息

• Unprecedented rearrangement during the formation of P–P homoatomic N-phosphino formamidine complexes
  作者：Thanh D. Le、Damien Arquier、Karinne Miqueu、Jean-Marc Sotiropoulos、Yannick Coppel、Stéphanie Bastin、Alain Igau

  DOI：10.1016/j.jorganchem.2008.10.033

  日期：2009.1

  A variety of homoatomic P-P donor-acceptor homoleptic (R=R') and heteroleptic (R not equal R') N-phosphino formamidine complexes [iPr(2)N-C(H)=N-PR2-PR'(2)]Cl were synthesized from the addition of N-phosphino formamidine (phosfam) donor reagent iPr(2)N-C(H)=N-PR2 on halogenophosphane compounds R'2PCl which are synthetic sources for the corresponding phosphenium derivatives R2P+. We have demonstrated that the dynamic equilibrium observed between the different species is shifted either completely to the side of the free species or to the side of the donor-acceptor adduct [iPr(2)N-C(H)=N-PPh2-PPh2]Cl by changing the solvent or by varying the temperature. Activation parameters of Delta S-not equal = (-130 +/- 7.2) J mol K-1 (1), Delta H-not equal = (8.4 +/- 0.6) kJ mol (1) and Delta G(not equal) (298.15 K) = (53.6 +/- 2.3) kJ mol (1) were determined by an Eyring analysis over the temperature range of 193-293 K. The negative entropy of activation is consistent with an associative pathway and the low value of Delta H-not equal suggests that the energy barrier for this reaction is entropically controlled. Phosphine-phosphenium adducts is the most appropriate term to describe the dynamic process observed at variable temperature for complexes [iPr(2)N-C(H)=N-PR2 -> PR'(2)](+), but the P-31 NMR chemical shift and the calculated electronic charges are more in favor of a phosphinophosphonium Lewis drawing [iPr(2)N-C(H)=N-PR2-PR'(2)](+). Formation of the homoatomic P - P heteroleptic formamidine complexes [iPr(2)N-C(H)=NPR'2PR2]Cl (R=Ph, R'=Et, iPr) results in the formal insertion of the phosphino group of the corresponding alkyl chlorophosphanes R'2PCl into the N-P bond of the starting phosfam ligand iPr(2)N-C(H)=N-PR2. Computed data are in agreement with the transient formation of a heteroatomic N-P intermediate [iPr(2)N-C(H)=N(PR2)PR'(2)]Cl, which then rearranges to the more thermodynamically favored homoatomic P-P compound [iPr(2)N-C(H)=N-PR2-PR'2] Cl. (C) 2008 Elsevier B. V. All rights reserved.