N-(2-ditert-butylphosphanylcyclopenten-1-yl)-2,6-di(propan-2-yl)aniline | 433976-49-9

• 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: N-(2-ditert-butylphosphanylcyclopenten-1-yl)-2,6-di(propan-2-yl)aniline
• CAS: 433976-49-9
• 化学式: C₂₅H₄₂NP
• 分子量: 387.589
• InChiKey: YWRLGEWVVJPFEF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.5
• 重原子数：
  27
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  乙二醇二甲醚溴化镍 、 N-(2-ditert-butylphosphanylcyclopenten-1-yl)-2,6-di(propan-2-yl)aniline 以 二氯甲烷 为溶剂， 以45%的产率得到[NiBr₂(((CH₃)2CH)2C₆H₃N(CH(CH₂)3C)P(C(CH₃)3)2)]
  参考文献：
  名称：

  Synthesis of New Phosphine Imine Ligands and Their Effects on the Thermal Stability of Late-Transition-Metal Olefin Polymerization Catalysts

  摘要：

  A series of a-phosphine imine hybrid ligands was successfully synthesized by nucleophilic substitution of di-tert-butylchlorophosphine or diphenylehlorophosphine on imine anions. These ligands exist as a-phosphine enamines before complexation, which tautomerize to a-phosphine imines upon coordination to Ni(II) or Pd(II). The Ni(II) and Pd(II) complexes with these PAN ligands were prepared and fully characterized by NMR, elemental analysis, and single-crystal X-ray crystallography. While all the Ni(II)-Pboolean ANDN complexes assume tetrahedral coordination geometry, the Pd(II)-PAN complexes are square planar. Upon activation with MAO, the Ni(II) complexes were active for ethylene polymerization. Whereas the Ni(II)-Pboolean ANDN complexes are less productive than the Brookhart Ni(II)-alpha-bis(imine) complexes and form polyethylenes with relatively low molecular weight, the thermal stabilities of these complexes upon activation are significantly higher than those of the corresponding Ni(II)-a-bis(imine) complexes. C-13 NMR shows that the polyethylenes are highly branched and have branch-on-branches. In contrast, the Pd(II)-Pboolean ANDN complexes were inactive for ethylene polymerization.

  DOI：

  10.1021/om020240i
• 作为产物：
  描述：

  二叔丁基氯化膦 、 N-cyclopentylidene-2,6-diisopropylaniline 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以27%的产率得到N-(2-ditert-butylphosphanylcyclopenten-1-yl)-2,6-di(propan-2-yl)aniline
  参考文献：
  名称：

  Ruthenium Complexes Stabilized by Bidentate Enamido-Phosphine Ligands: Aspects of Cooperative H₂ Activation

  摘要：

  Four bidentate, hybrid ligands ((R)(NP)(R)'H) featuring imine-nitrogen and alkyl-phosphine donors linked by a cyclopentyl ring were synthesized. The ortho position of the aryl group attached to nitrogen is varied such that R is Me or Pr-i; additionally, the groups decorating phosphorus (R') are varied between Bu-t or Pr-i. The addition of each ligand to RuHCl(PPr3i)(2)(CO) in the presence of KOBut generates four enamido-phosphine complexes RuH{(R)(NP)(R)'(PPr3i)(CO) that were characterized by NMR spectroscopy, elemental analyses, and, in the case of R = Pr-i and R' = Bu-t or Pr-i, X-ray crystallography. Depending on R', the reaction of RuH{(R)(NP)(R)'}(PPr3i)(CO) with H-2 generates varying amounts of the iminephosphine complex RuH2{(R)(NP)(R)'H}(PPr3i)(CO). Insights into the mechanism of H-2 activation by these enamido derivatives were explored using RuH{(Pr)(NP)(Pri)(PPr3i)(CO), for which an intermediate was identified as the dihydrogen-dihydride complex, RuH2(H-2){(Pri)(NP)H-Pri}(PPr3i)(CO), on the basis of the T-1,T-min value of 22 ms for the H-1 NMR resonance at delta -7.2 at 238 K (measured at 400 MHz). The N donor of the enamine tautomeric form of the ligand is protonated by H-2 or D-2 and dissociates from Ru. Tautomerization of the enamine to the imine form of the dissociated arm is involved in formation of the final product.

  DOI：

  10.1021/acs.inorgchem.5b00672

文献信息

• Ruthenium Complexes Stabilized by Bidentate Enamido-Phosphine Ligands: Aspects of Cooperative H₂ Activation
  作者：Truman C. Wambach、Michael D. Fryzuk

  DOI：10.1021/acs.inorgchem.5b00672

  日期：2015.6.15

  Four bidentate, hybrid ligands ((R)(NP)(R)'H) featuring imine-nitrogen and alkyl-phosphine donors linked by a cyclopentyl ring were synthesized. The ortho position of the aryl group attached to nitrogen is varied such that R is Me or Pr-i; additionally, the groups decorating phosphorus (R') are varied between Bu-t or Pr-i. The addition of each ligand to RuHCl(PPr3i)(2)(CO) in the presence of KOBut generates four enamido-phosphine complexes RuH(R)(NP)(R)'(PPr3i)(CO) that were characterized by NMR spectroscopy, elemental analyses, and, in the case of R = Pr-i and R' = Bu-t or Pr-i, X-ray crystallography. Depending on R', the reaction of RuH(R)(NP)(R)'}(PPr3i)(CO) with H-2 generates varying amounts of the iminephosphine complex RuH2(R)(NP)(R)'H}(PPr3i)(CO). Insights into the mechanism of H-2 activation by these enamido derivatives were explored using RuH(Pr)(NP)(Pri)(PPr3i)(CO), for which an intermediate was identified as the dihydrogen-dihydride complex, RuH2(H-2)(Pri)(NP)H-Pri}(PPr3i)(CO), on the basis of the T-1,T-min value of 22 ms for the H-1 NMR resonance at delta -7.2 at 238 K (measured at 400 MHz). The N donor of the enamine tautomeric form of the ligand is protonated by H-2 or D-2 and dissociates from Ru. Tautomerization of the enamine to the imine form of the dissociated arm is involved in formation of the final product.
• Synthesis of New Phosphine Imine Ligands and Their Effects on the Thermal Stability of Late-Transition-Metal Olefin Polymerization Catalysts
  作者：Zhibin Guan、William J. Marshall

  DOI：10.1021/om020240i

  日期：2002.8.19

  A series of a-phosphine imine hybrid ligands was successfully synthesized by nucleophilic substitution of di-tert-butylchlorophosphine or diphenylehlorophosphine on imine anions. These ligands exist as a-phosphine enamines before complexation, which tautomerize to a-phosphine imines upon coordination to Ni(II) or Pd(II). The Ni(II) and Pd(II) complexes with these PAN ligands were prepared and fully characterized by NMR, elemental analysis, and single-crystal X-ray crystallography. While all the Ni(II)-Pboolean ANDN complexes assume tetrahedral coordination geometry, the Pd(II)-PAN complexes are square planar. Upon activation with MAO, the Ni(II) complexes were active for ethylene polymerization. Whereas the Ni(II)-Pboolean ANDN complexes are less productive than the Brookhart Ni(II)-alpha-bis(imine) complexes and form polyethylenes with relatively low molecular weight, the thermal stabilities of these complexes upon activation are significantly higher than those of the corresponding Ni(II)-a-bis(imine) complexes. C-13 NMR shows that the polyethylenes are highly branched and have branch-on-branches. In contrast, the Pd(II)-Pboolean ANDN complexes were inactive for ethylene polymerization.