(E)-N'-(diethylphosphaneyl)-N,N-diisopropylformimidamide | 1123554-23-3

• 分子结构分类: 有机化合物 - 有机磷化合物
• 英文名称: (E)-N'-(diethylphosphaneyl)-N,N-diisopropylformimidamide
• CAS: 1123554-23-3
• 化学式: C₁₁H₂₅N₂P
• 分子量: 216.307
• InChiKey: WBUOFIUXDGMCBE-FMIVXFBMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.57
• 重原子数：
  14.0
• 可旋转键数：
  6.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  15.6
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  (E)-N'-(diethylphosphaneyl)-N,N-diisopropylformimidamide 、 二苯基氯化膦 以 二氯甲烷 为溶剂， 反应 0.08h， 生成
  参考文献：
  名称：

  Unprecedented rearrangement during the formation of P–P homoatomic N-phosphino formamidine complexes

  摘要：

  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.

  DOI：

  10.1016/j.jorganchem.2008.10.033
• 作为产物：
  描述：

  氯化二乙基磷 、 二异丙基氨腈 在 Schwartz's reagent 作用下， 以 二氯甲烷 为溶剂， 以85%的产率得到(E)-N'-(diethylphosphaneyl)-N,N-diisopropylformimidamide
  参考文献：
  名称：

  Unprecedented rearrangement during the formation of P–P homoatomic N-phosphino formamidine complexes

  摘要：

  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.

  DOI：

  10.1016/j.jorganchem.2008.10.033