Ph2PN(nPr)PPhN(nPr)H | 1268490-79-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: Ph2PN(nPr)PPhN(nPr)H
• 英文别名: N-[[diphenylphosphanyl(propyl)amino]-phenylphosphanyl]propan-1-amine
• CAS: 1268490-79-4
• 化学式: C₂₄H₃₀N₂P₂
• 分子量: 408.463
• InChiKey: ROZVDVRKAVBAHO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.3
• 重原子数：
  28
• 可旋转键数：
  10
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  15.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  苯基二氯化磷 在 三乙胺 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 19.0h， 生成 Ph2PN(nPr)PPhN(nPr)H
  参考文献：
  名称：

  N,N′-Bis(diphenylphosphino)diaminophenylphosphine Ligands for Chromium-Catalyzed Selective Ethylene Oligomerization Reactions

  摘要：

  Reaction of 1 or 2 equiv of Ph2PCl with PhP(N(H)R)(2) (R = n-propyl) yields Ph2PN(R)P(Ph)N(R)H (1) or Ph2PN(R)P(Ph)N(R)PPh2 (2), respectively. In contrast, reaction of 1 or 2 equiv of Ph2PCl with PhP(N(H)R)(2) (R = isopropyl) yields exclusively Ph2PN(R)P(Ph)N(R)H (3), even under more forcing conditions. Low-temperature NMR spectroscopy and a conformational analysis of Ph2PN-(iPr)P(Ph)N(iPr)H (3) reveal the lowest energy conformer to have a close N-H center dot center dot center dot P interaction of 2.95 angstrom, which we speculate may hinder further reactivity of this molecule. Reaction of 3 with [Cr(CO)(6)] yields [Cr(3)(CO)(4)] (5), which has been structurally characterized. Coordination of ligand 3 facilitates its conversion to Ph2PN(iPr)P(Ph)N(iPr)PPh2 (4) while bound to chromium, yielding the complex [Cr(4)(CO)(4)] (6), which has also been structurally characterized. Ligands 1 and 2, when reacted in situ with [Cr(acac)(3)] (acac = acetylacetonate) and modified methylalumoxane, and complexes 5 and 6, when activated with Ag[Al(OC4F9)(4)] and triethylaluminum, are moderately active and selective catalysts for the selective oligomerization of ethene to 1-hexene and 1-octene.

  DOI：

  10.1021/om100912y

文献信息

• <i>N</i>,<i>N</i>′-Bis(diphenylphosphino)diaminophenylphosphine Ligands for Chromium-Catalyzed Selective Ethylene Oligomerization Reactions
  作者：Arminderjit Dulai、Claire L. McMullin、Kenny Tenza、Duncan F. Wass

  DOI：10.1021/om100912y

  日期：2011.3.14

  Reaction of 1 or 2 equiv of Ph2PCl with PhP(N(H)R)(2) (R = n-propyl) yields Ph2PN(R)P(Ph)N(R)H (1) or Ph2PN(R)P(Ph)N(R)PPh2 (2), respectively. In contrast, reaction of 1 or 2 equiv of Ph2PCl with PhP(N(H)R)(2) (R = isopropyl) yields exclusively Ph2PN(R)P(Ph)N(R)H (3), even under more forcing conditions. Low-temperature NMR spectroscopy and a conformational analysis of Ph2PN-(iPr)P(Ph)N(iPr)H (3) reveal the lowest energy conformer to have a close N-H center dot center dot center dot P interaction of 2.95 angstrom, which we speculate may hinder further reactivity of this molecule. Reaction of 3 with [Cr(CO)(6)] yields [Cr(3)(CO)(4)] (5), which has been structurally characterized. Coordination of ligand 3 facilitates its conversion to Ph2PN(iPr)P(Ph)N(iPr)PPh2 (4) while bound to chromium, yielding the complex [Cr(4)(CO)(4)] (6), which has also been structurally characterized. Ligands 1 and 2, when reacted in situ with [Cr(acac)(3)] (acac = acetylacetonate) and modified methylalumoxane, and complexes 5 and 6, when activated with Ag[Al(OC4F9)(4)] and triethylaluminum, are moderately active and selective catalysts for the selective oligomerization of ethene to 1-hexene and 1-octene.