tricarbonyl(bis(di(o-N-methylanilinyl)phosphino)methane)ruthenium(0) | 1224509-17-4

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: tricarbonyl(bis(di(o-N-methylanilinyl)phosphino)methane)ruthenium(0)
• 英文别名: [Ru(CO)3(P,P'-bis(di(o-N-methylanilinyl)phosphino)methane)]；[Ru(CO)3(P,P'-mapm)]；2-[bis[2-(methylamino)phenyl]phosphanylmethyl-[2-(methylamino)phenyl]phosphanyl]-N-methylaniline;carbon monoxide;ruthenium
• CAS: 1224509-17-4
• 化学式: C₃₂H₃₄N₄O₃P₂Ru
• 分子量: 685.664
• InChiKey: WANWBPMRRBMDNC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.26
• 重原子数：
  42
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.16
• 拓扑面积：
  51.1
• 氢给体数：
  4
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  [RhCl(μ-Cl)(CO)2]2 、 tricarbonyl(bis(di(o-N-methylanilinyl)phosphino)methane)ruthenium(0) 以 not given 为溶剂， 以0%的产率得到[RhRuCl(CO)3(μ-CO)(μ-P,N,P',N'-mapm)]
  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
• 作为产物：
  描述：

  tetracarbonyl(bis(di(o-N-methylanilinyl)phosphino)methane)ruthenium(0) 以 not given 为溶剂， 生成 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