carbanide;2-di(propan-2-yl)phosphanyl-N-[2-di(propan-2-yl)phosphanylethyl]ethanamine;palladium(2+);hexafluorophosphate | 1140920-83-7

• 分子结构分类: 有机化合物 - 有机磷化合物
• 英文名称: carbanide;2-di(propan-2-yl)phosphanyl-N-[2-di(propan-2-yl)phosphanylethyl]ethanamine;palladium(2+);hexafluorophosphate
• CAS: 1140920-83-7
• 化学式: C₁₇H₄₀NP₂Pd*F₆P
• 分子量: 571.843
• InChiKey: QWERSLMIVRBZEX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.0
• 重原子数：
  28
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  carbanide;2-di(propan-2-yl)phosphanyl-N-[2-di(propan-2-yl)phosphanylethyl]ethanamine;palladium(2+);hexafluorophosphate 在 KO-t-Bu 作用下， 以 四氢呋喃 为溶剂， 以62%的产率得到bis[2-di(propan-2-yl)phosphanylethyl]azanide;carbanide;palladium(2+)
  参考文献：
  名称：

  Palladium N(CH₂CH₂PⁱPr₂)₂-Dialkylamides: Synthesis, Structural Characterization, and Reactivity

  摘要：

  Palladium(II) aminodiphosphine PNP pincer complexes [PdR(PNPH]PF6 (1(R); R = Cl Me, Ph; PNPH = HN((CH2CH2PPr2)-Pr-i)(2)) were prepared. Deprotonation with (KOBu)-Bu-t affords dialkylamides [PdR(PNP)] (2(R); R = Cl Me, Ph; PNP = ((NCH2CH2PPr2)-Pr-i)(2)) in high yield which are stable toward beta-H elimination. While AgPF6 oxidizes the amides, cationic amido complexes [PdL(PNP)]PF6 (3(L); L = (CNBu)-Bu-t, PMe3) were obtained upon chloride abstraction from 1(Cl) with TIPF6. The reaction of amide 2(Cl) with MeOTf results in N-methylation yielding [PdCl(PNPMe)]OTf (5) quantitatively. N-H acidities of the amino complexes 1(Me) (pK(a) = 24.2(1)) and 1(Ph) (pK(a) = 23.2(1)) were determined in dmso. Complexes 1(Cl), 1(Me), 2(Cl) 2(Me), 3(CNf8u), and 5 were structurally characterized by single crystal X-ray diffraction. The amido complexes feature pyramidal nitrogen atoms in the solid state. The molecular structures, high N-basicity, and reactivity of the amido complexes can be explained with Pd-N-amido bonding that is characterized by strong N -> Pd sigma-donation and repulsive d(pi)-p(pi) pi-interactions. This interpretation was confirmed by density functional theory (DFT) calculations of 2(Cl).

  DOI：

  10.1021/ic802286u
• 作为产物：
  描述：

  2-di(propan-2-yl)phosphanyl-N-[2-di(propan-2-yl)phosphanylethyl]ethanamine;palladium(2+);chloride;hexafluorophosphate 、 甲基溴化镁 以 四氢呋喃 为溶剂， 以95%的产率得到carbanide;2-di(propan-2-yl)phosphanyl-N-[2-di(propan-2-yl)phosphanylethyl]ethanamine;palladium(2+);hexafluorophosphate
  参考文献：
  名称：

  Palladium N(CH₂CH₂PⁱPr₂)₂-Dialkylamides: Synthesis, Structural Characterization, and Reactivity

  摘要：

  Palladium(II) aminodiphosphine PNP pincer complexes [PdR(PNPH]PF6 (1(R); R = Cl Me, Ph; PNPH = HN((CH2CH2PPr2)-Pr-i)(2)) were prepared. Deprotonation with (KOBu)-Bu-t affords dialkylamides [PdR(PNP)] (2(R); R = Cl Me, Ph; PNP = ((NCH2CH2PPr2)-Pr-i)(2)) in high yield which are stable toward beta-H elimination. While AgPF6 oxidizes the amides, cationic amido complexes [PdL(PNP)]PF6 (3(L); L = (CNBu)-Bu-t, PMe3) were obtained upon chloride abstraction from 1(Cl) with TIPF6. The reaction of amide 2(Cl) with MeOTf results in N-methylation yielding [PdCl(PNPMe)]OTf (5) quantitatively. N-H acidities of the amino complexes 1(Me) (pK(a) = 24.2(1)) and 1(Ph) (pK(a) = 23.2(1)) were determined in dmso. Complexes 1(Cl), 1(Me), 2(Cl) 2(Me), 3(CNf8u), and 5 were structurally characterized by single crystal X-ray diffraction. The amido complexes feature pyramidal nitrogen atoms in the solid state. The molecular structures, high N-basicity, and reactivity of the amido complexes can be explained with Pd-N-amido bonding that is characterized by strong N -> Pd sigma-donation and repulsive d(pi)-p(pi) pi-interactions. This interpretation was confirmed by density functional theory (DFT) calculations of 2(Cl).

  DOI：

  10.1021/ic802286u