N-(3-(diphenylphosphino)propyl)triphenylphisphinimine | 164356-59-6

• 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-(3-(diphenylphosphino)propyl)triphenylphisphinimine
• 英文别名: N-(3-(diphenylphosphino)propyl)triphenylphosphinimine；3-Diphenylphosphanylpropylimino(triphenyl)-lambda5-phosphane；3-diphenylphosphanylpropylimino(triphenyl)-λ5-phosphane
• CAS: 164356-59-6
• 化学式: C₃₃H₃₁NP₂
• 分子量: 503.563
• InChiKey: YATWEDUCHPJYQQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.9
• 重原子数：
  36
• 可旋转键数：
  9
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.09
• 拓扑面积：
  12.4
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  十羰基二铼 、 N-(3-(diphenylphosphino)propyl)triphenylphisphinimine 以 甲苯 为溶剂， 以92%的产率得到
  参考文献：
  名称：

  Synthesis and Coordination Chemistry of a Novel Phosphinimine Phosphine

  摘要：

  The incorporation of a phosphinimino moiety into phosphine ligands to form a new bidentate Ph(3)P=N(CH2)(3)PPh(2) (1) is reported. Compound 1 can act as a sigma-N and sigma-P donor ligand or react with metal carbonyls to form isocyanide complexes. Complexes of (CO)(4)M-(1-P,N) [M = Mo (2), W (3)] were prepared from the reaction of ET(4)N[M(CO)(5)Br] with 1 in refluxing THF solution, whereas the isocyanide complexes of (CO)(5)MCN(CH2)(3)PPh(2) [M = Cr (4), Mo (5), W (6)] are obtained from the reaction of M(CO)(6) with 1 at 25 degrees C. The deoxygenation nature is also shown in the reaction of CpFe(CO)(2)I, CpRu(CO)(2)I, Re(CO)(5)Br, and Re-2(CO)(10) with 1 to form the corresponding isocyanide complexes [CpFe(CO){CN(CH2)(3)-PPh(2)-C,P}]I (7), CpRu(CO)I{CN(CH2)(3)PPh(2)-C} (10), BrRe(CO)(5-n){CN(CH2)(3)PPh(2)-C}(n) {n = 1(12), 2 (14)], and Re-2(CO)(9){CN(CH2)(3)PPh(2)-C} (15), respectively. The free phosphine of 10 underwent exchange with one triphenylphosphine ligand in CpRu(PPh(3))(2)Cl to yield the binuclear species [CpRu(PPh(3))Cl{P(Ph(2))(CH2)(3)NC}Ru(CO)CpI] (11), whereas intramolecular ligand substitution occurred in both 12 and 15 to give Br(CO)(3)Re{CN(CH2)(3)PPh(2)-C,P} (13) and {mu-CN(CH2)(3)PPh(2)}Re-2(CO)(8) (16). Reaction of (COD)PdCl2 with 1 produced the complex (1-P,N)PdCl2 (18), in which 1 acts as a sigma-N, sigma-P bidentate ligand. X-ray crystal structural analysis of [CpFe(CO){CN(CH2)(3)PPh(2)-C,P}]PF6 (7a) and 18 confirmed the formulation of both complexes. The C=N bond distance [1.20(3) Angstrom] of 7a is greater than those in the related iron-isocyanide complexes; the angle C-N-C [141(2)degrees] deviates from 180 degrees, indicating that the resonance contribution of Fe=C=N- is more important than that of Fe-C=N-. These observations are consistent with spectral data, the smaller infrared stretching wavenumber (2089 cm(-1)), and the greater shift (C-13 NMR delta 183.7 ppm) of the isocyanide moiety of 7.

  DOI：

  10.1021/om00004a060

文献信息

• Phosphine-Tethered Carbene Ligands: Template Synthesis and Reactivity of Cyclic and Acyclic Functionalized Carbenes
  作者：Insun Yu、Christopher J. Wallis、Brian O. Patrick、Paula L. Diaconescu、Parisa Mehrkhodavandi

  DOI：10.1021/om100841j

  日期：2010.11.22

  and isopropoxide to form the corresponding ylidene complexes CpFe(CO)(PCO(X)N) (X = Me (11), Et (12), i-Pr (13)), which, in the second step, can be protonated with an equimolar amount of HBF4 to form acyclic (oxy)(amino)carbene complexes [CpFe(CO)(PCO(X)NH)]BF4 (X = Me (14), Et (15), i-Pr (16)). Five and six-membered cyclic (oxy)(amino)carbene complexes [CpFe(CO)(PCNO-nCy)]Cl (n = 5 (17), 6 (18)) are

  膦系异氰酸铁（II）配合物1 [CpFe（CO）（PCN）] I与伯胺和仲胺的反应形成相应的无环（二氨基）卡宾配合物[CpFe（CO）（PCXNH）] I；X ＝正丁胺（4），4-甲基苯胺（5），二己胺（6）。从1与2的反应分两个步骤生成五元和六元环状（二氨基）卡宾络合物[CpFe（CO）（PCNHN- n Cy）] I（n = 5（9），6（10））-氯乙基和3-氯丙胺，首先形成无环二氨基卡宾络合物[CpFe（CO）（PC NX NH）] I（X =氯乙基（7），氯丙基（8））分别进行去质子化和分子内环化。这种方法学对酒精无效；然而，无环（氧）（氨基）卡宾络合物是通过1与甲醇钾，乙醇盐和异丙醇钾反应形成相应的亚烷基络合物CpFe（CO）（PC O（X） N）而分两步生成的（X = Me（11），Et（12），i -Pr（13）），可以在第二步中用等摩尔量的HBF 4对其进行质子化，形成无