bis(di(o-N-methylanilinyl)phosphino)methane | 1172577-78-4

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: bis(di(o-N-methylanilinyl)phosphino)methane
• 英文别名: mapm；2-[bis[2-(methylamino)phenyl]phosphanylmethyl-[2-(methylamino)phenyl]phosphanyl]-N-methylaniline
• CAS: 1172577-78-4
• 化学式: C₂₉H₃₄N₄P₂
• 分子量: 500.563
• InChiKey: WZBBHJRZBILCAF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  35
• 可旋转键数：
  10
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  48.1
• 氢给体数：
  4
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  [Ru(CO)4(η2-ethylene)] 、 bis(di(o-N-methylanilinyl)phosphino)methane 以 二氯甲烷 为溶剂， 以89%的产率得到tricarbonyl(bis(di(o-N-methylanilinyl)phosphino)methane)ruthenium(0)
  参考文献：
  名称：

  Coordinatively Diverse ortho-Phosphinoaniline Complexes of Ruthenium and Isolation of a Putative Intermediate in Ketone Transfer Hydrogenation Catalysis

  摘要：

  Amine-functionalized mono- and diphosphines have been used to prepare a series of ruthenium complexes which exhibit a variety of coordination modes depending on the number of donors possessed by the ligands, the degree of amine methylation, the solvent system used, and the oxidation state of the metal Reactions of the monophosphinoanilines, Ph2PAr or Ph2PAr' (Ar = o-C6H4NHMe, Ar' = o-C6H4NMe2), with 0.5 equiv of [RuCl(mu-Cl)(eta(6)-p-cymene)](2) in dichloromethane result in the formation of [RuCl2(eta(6)-p-cymene)(P-Ph2PAr)] or [RuCl(eta(6)-p-cymene)(P,N-Ph2PAr')]Cl, respectively In refluxing methanol, [RuCl2(eta(6)-p-cymene)(P-Ph2PAr)] gradually undergoes chloride ion dissociation to afford the P,N-chelate, [RuCl(eta(6)-p-cymene)(P,N-Ph2PAr)]Cl. This chelate can then be deprotonated to afford the amido complex, [RuCl(eta(6)-p-cymene)(P,N-Ph2PAr-)] (Ar = o-C6H4NMe-), which is an active ketone transfer hydrogenation catalyst. Reactions of the diphosphines, Ar2PCH2PAr2 (mapm) or Ar'2PCH2PAr'(2) (dmapm) with 0.5 equiv of [RuCl(mu-Cl)(eta(6)-p-cymene)](2) result in the formation of [RuCl2(P,P',N,N'-mapm)] or [RuCl(eta(6)-p-cymene)(P,P'-dmapm)]Cl, respectively, in which increased methyl substitution in the latter actually inhibits amine coordination with retention of the p-cymene fragment. Reaction of mapm with 1 equiv of [Ru(CO)(4)(eta(2)-C2H4)] in dichloromethane initially produces [Ru(CO)(4)(P-mapm)] which, over a 24 h period with exposure to ambient light, is completely converted to the P,P'-chelate, [Ru(CO)(3)(P,P'-mapm)], by photodissociation of carbon monoxide. The same reaction with 2 equiv of [Ru(CO)(4)(eta(2)-C2H4)] generates a mixture of [Ru-3(CO)(10)(mu-P,P'-mapm)] and the mononuclear P,P'-chelate The trinuclear complex can also be synthesized by direct reaction of mapm with 1 equiv of [Ru-3(CO)(12)]

  DOI：

  10.1021/ic100165t

文献信息

• Mono- and binuclear complexes of rhodium involving a new series of hemilabile o-phosphinoaniline ligands
  作者：Lindsay J. Hounjet、Matthias Bierenstiel、Michael J. Ferguson、Robert McDonald、Martin Cowie

  DOI：10.1039/b822170g

  日期：——

  and/or bridging P,N-ligands within mono- and binuclear rhodium(i) complexes, respectively. The previously prepared phosphines, Ph(x)PAr'(3-x) (x = 0, 1 or 2, Ar' = o-N,N-dimethylanilinyl) and Ar'(2)PCH(2)PAr'(2) (dmapm), have also been used to prepare analogous mono- and binuclear complexes. Variable temperature (1)H NMR spectroscopy of the mononuclear complexes, [RhCl(CO)(L)] (L = PhPAr(2), PhPAr'(2),

  Ph（x）PAr（3-x）类型的单膦（x = 0、1或2，Ar = oN-甲基苯胺基）和二膦Ar（2）PCH（2）PAr（2）（mapm）合成用作螯合和/或桥接单核和双核铑（i）配合物中的P，N-配体。先前制备的膦Ph（x）PAr'（3-x）（x = 0、1或2，Ar'= oN，N-二甲基苯胺基）和Ar'（2）PCH（2）PAr'（2）（ dmapm），也已用于制备类似的单核和双核复合物。单核络合物[RhCl（CO）（L）]（L = PhPAr（2），PhPAr'（2），PAr（3）和PAr'（3））和线的可变温度（1）H NMR光谱所得光谱的形状分析表明，相对于相关的单甲基苯胺基，N，N-二甲基苯胺基供体的不稳定性显着增加。单核络合物的X射线结构分析表明，与它们的单甲基类似物相比，二甲基苯胺基络合物的II型半透性增强是由于涉及配位的二甲基苯胺基取代基的空间相互作用增加。在双核，dmapm
• Comparison of Structure and Reactivity of Phosphine-Amido and Hemilabile Phosphine-Amine Chelates of Rhodium
  作者：Lindsay J. Hounjet、Robert McDonald、Michael J. Ferguson、Martin Cowie

  DOI：10.1021/ic101883u

  日期：2011.6.20

  with oxygen to form the peroxo complex, [RhO2(P,P′-dppe)(P,N-Ph2PAr–)], and with iodomethane to yield [RhI(CH3)(P,P′-dppe)(P,N-Ph2PAr–)]. Hemilabile phosphine-amine compounds can also be prepared by reactions of [Rh(P,P′-dppe)(P,N-Ph2PAr–)] with Me3OBF4 or HBF4·Et2O, resulting in (thermodynamic) additions at nitrogen to form [Rh(P,P′-dppe)(P,N-Ph2PAr′)][BF4] or [Rh(P,P′-dppe)(P,N-Ph2PAr)][BF4], respectively

  合成了一系列带有正膦基苯胺基和正膦基苯胺配体的单核和双核铑（I）配合物。质子单膦基苯胺Ph 2 PAr或PhPAr 2（Ar = o -C 6 H 4 NHMe）与0.5当量的[Rh（μ-OMe）（COD）] 2的反应导致形成中性酰胺基络合物， [Rh（COD）（P，N -Ph 2 PAr –）]或[Rh（COD）（P，N -PhP（Ar –）Ar）]（Ar – = o -C 6H 4 NMe –）分别通过内部甲醇离子对胺进行化学计量控制的去质子化。类似地，双核配合物，铑[Rh 2（COD）2（μ- P，Ñ，P' ，N' -mapm 2- ）]（MAPM 2- =分析纯（AR -）PCH 2 P（氩- ）中的Ar） ，可以通过质子二膦基苯胺，mapm（Ar 2 PCH 2 PAr 2）与1当量的[Rh（μ-OMe）（COD）] 2反应制备。可以通过monophosphinoanilines
• Coordinatively Diverse <i>ortho</i>-Phosphinoaniline Complexes of Ruthenium and Isolation of a Putative Intermediate in Ketone Transfer Hydrogenation Catalysis
  作者：Lindsay J. Hounjet、Matthias Bierenstiel、Michael J. Ferguson、Robert McDonald、Martin Cowie

  DOI：10.1021/ic100165t

  日期：2010.5.3

  Amine-functionalized mono- and diphosphines have been used to prepare a series of ruthenium complexes which exhibit a variety of coordination modes depending on the number of donors possessed by the ligands, the degree of amine methylation, the solvent system used, and the oxidation state of the metal Reactions of the monophosphinoanilines, Ph2PAr or Ph2PAr' (Ar = o-C6H4NHMe, Ar' = o-C6H4NMe2), with 0.5 equiv of [RuCl(mu-Cl)(eta(6)-p-cymene)](2) in dichloromethane result in the formation of [RuCl2(eta(6)-p-cymene)(P-Ph2PAr)] or [RuCl(eta(6)-p-cymene)(P,N-Ph2PAr')]Cl, respectively In refluxing methanol, [RuCl2(eta(6)-p-cymene)(P-Ph2PAr)] gradually undergoes chloride ion dissociation to afford the P,N-chelate, [RuCl(eta(6)-p-cymene)(P,N-Ph2PAr)]Cl. This chelate can then be deprotonated to afford the amido complex, [RuCl(eta(6)-p-cymene)(P,N-Ph2PAr-)] (Ar = o-C6H4NMe-), which is an active ketone transfer hydrogenation catalyst. Reactions of the diphosphines, Ar2PCH2PAr2 (mapm) or Ar'2PCH2PAr'(2) (dmapm) with 0.5 equiv of [RuCl(mu-Cl)(eta(6)-p-cymene)](2) result in the formation of [RuCl2(P,P',N,N'-mapm)] or [RuCl(eta(6)-p-cymene)(P,P'-dmapm)]Cl, respectively, in which increased methyl substitution in the latter actually inhibits amine coordination with retention of the p-cymene fragment. Reaction of mapm with 1 equiv of [Ru(CO)(4)(eta(2)-C2H4)] in dichloromethane initially produces [Ru(CO)(4)(P-mapm)] which, over a 24 h period with exposure to ambient light, is completely converted to the P,P'-chelate, [Ru(CO)(3)(P,P'-mapm)], by photodissociation of carbon monoxide. The same reaction with 2 equiv of [Ru(CO)(4)(eta(2)-C2H4)] generates a mixture of [Ru-3(CO)(10)(mu-P,P'-mapm)] and the mononuclear P,P'-chelate The trinuclear complex can also be synthesized by direct reaction of mapm with 1 equiv of [Ru-3(CO)(12)]