methyl 2-(bis(diphenylphosphinomethyl)amino)acetate | 92752-30-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: methyl 2-(bis(diphenylphosphinomethyl)amino)acetate
• 英文别名: Methyl 2-[bis(diphenylphosphanylmethyl)amino]acetate
• CAS: 92752-30-2
• 化学式: C₂₉H₂₉NO₂P₂
• 分子量: 485.502
• InChiKey: QMUOZKPATJGIBN-UHFFFAOYSA-N

物化性质

• 沸点：
  580.0±45.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  34
• 可旋转键数：
  11
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  bis(1,5-cyclooctadiene)rhodium(I) trifluoromethanesulfonate 、 methyl 2-(bis(diphenylphosphinomethyl)amino)acetate 以 四氢呋喃 为溶剂， 反应 12.0h， 以69%的产率得到[Rh(PN^Gly-OMeP)₂]+
  参考文献：
  名称：

  The Influence of the Second and Outer Coordination Spheres on Rh(diphosphine)₂ CO₂ Hydrogenation Catalysts

  摘要：

  A series of [Rh((PCH2XCH2P)-C-R)(2)](+) complexes was prepared to investigate second and outer coordination sphere effects on CO2 hydrogenation catalysis, where X is CH2 (dppp) or X-R is N-CH3, N-CH2COOH (glycine), N-CH2COOCH3 (Gly-OMe), or N-CH2C(O)N-CH(CH3)-COOCH3 (GlyAla-OMe). All of these complexes were active for CO2 reduction to formate, with the N-CH3 derivative offering an 8-fold enhancement over the dppp derivative, which is consistent with increased electron density around the metal. Despite the increase in rate with the addition of the pendant nitrogen, the addition of electron withdrawing amino acids and dipeptides to the amine resulted in complexes with reductions in rate of 1 to 2 orders of magnitude, most consistent with a change in pK(a) of the pendant amine, resulting in lower activity. Collectively, the data suggest multiple contributions of the pendant amine in this catalytic system.

  DOI：

  10.1021/cs5009199
• 作为产物：
  描述：

  甘氨酸甲酯盐酸盐 、 (二苯基膦基)甲醇 以 乙醇 、 水 为溶剂， 反应 2.0h， 以2.4 g的产率得到methyl 2-(bis(diphenylphosphinomethyl)amino)acetate
  参考文献：
  名称：

  Catalytic Hydrogen Evolution by Fe(II) Carbonyls Featuring a Dithiolate and a Chelating Phosphine

  摘要：

  Two pentacoordinate mononudear iron carbonyls of the form (bdt)Fe(CO)P-2 [bdt = benzene-1,2-dithiolate; P-2 = 1,1'-diphenylphosphinoferrocene (1) or methyl-2-{bis(diphenylphosphinomethyl)amino}acetate (2)] were prepared as functional, biomimetic models for the distal iron (Fe-d) of the active site of [FeFe]-hydrogenase. X-ray crystal structures of the complexes reveal that, despite similar v(CO) stretching band frequencies, the two complexes have different coordination geometries. In X-ray crystal structures, the iron center of 1 is in a distorted trigonal bipyramidal arrangement, and that of 2 is in a distorted square pyramidal geometry. Electrochemical investigation shows that both complexes catalyze electrochemical proton reduction from acetic acid at mild overpotential, 0.17 and 0.38 V for 1 and 2, respectively. Although coordinatively unsaturated, the complexes display only weak, reversible binding affinity toward CO (1 bar). However, ligand centered protonation by the strong acid, HBF4 center dot OEt2, triggers quantitative CO uptake by 1 to form a dicarbonyl analogue [1(H)-CO](+) that can be reversibly converted back to 1 by deprotonation using NEt3. Both crystallographically determined distances within the bdt ligand and density functional theory calculations suggest that the iron centers in both 1 and 2 are partially reduced at the expense of partial oxidation of the bdt ligand. Ligand protonation interrupts this extensive electronic delocalization between the Fe and bdt making 1(H)(+) susceptible to external CO binding.

  DOI：

  10.1021/ic5012988

文献信息

• KELLNER, K.;HANKE, W.;TZSCHACH, A., Z. CHEM., 1984, 24, N 5, 193-194
  作者：KELLNER, K.、HANKE, W.、TZSCHACH, A.

  DOI：——

  日期：——
• Catalytic Hydrogen Evolution by Fe(II) Carbonyls Featuring a Dithiolate and a Chelating Phosphine
  作者：Souvik Roy、Shobeir K. S. Mazinani、Thomas L. Groy、Lu Gan、Pilarisetty Tarakeshwar、Vladimiro Mujica、Anne K. Jones

  DOI：10.1021/ic5012988

  日期：2014.9.2

  Two pentacoordinate mononudear iron carbonyls of the form (bdt)Fe(CO)P-2 [bdt = benzene-1,2-dithiolate; P-2 = 1,1'-diphenylphosphinoferrocene (1) or methyl-2-bis(diphenylphosphinomethyl)amino}acetate (2)] were prepared as functional, biomimetic models for the distal iron (Fe-d) of the active site of [FeFe]-hydrogenase. X-ray crystal structures of the complexes reveal that, despite similar v(CO) stretching band frequencies, the two complexes have different coordination geometries. In X-ray crystal structures, the iron center of 1 is in a distorted trigonal bipyramidal arrangement, and that of 2 is in a distorted square pyramidal geometry. Electrochemical investigation shows that both complexes catalyze electrochemical proton reduction from acetic acid at mild overpotential, 0.17 and 0.38 V for 1 and 2, respectively. Although coordinatively unsaturated, the complexes display only weak, reversible binding affinity toward CO (1 bar). However, ligand centered protonation by the strong acid, HBF4 center dot OEt2, triggers quantitative CO uptake by 1 to form a dicarbonyl analogue [1(H)-CO](+) that can be reversibly converted back to 1 by deprotonation using NEt3. Both crystallographically determined distances within the bdt ligand and density functional theory calculations suggest that the iron centers in both 1 and 2 are partially reduced at the expense of partial oxidation of the bdt ligand. Ligand protonation interrupts this extensive electronic delocalization between the Fe and bdt making 1(H)(+) susceptible to external CO binding.
• The Influence of the Second and Outer Coordination Spheres on Rh(diphosphine)₂ CO₂ Hydrogenation Catalysts
  作者：J. Timothy Bays、Nilusha Priyadarshani、Matthew S. Jeletic、Elliot B. Hulley、Deanna L. Miller、John C. Linehan、Wendy J. Shaw

  DOI：10.1021/cs5009199

  日期：2014.10.3

  A series of [Rh((PCH2XCH2P)-C-R)(2)](+) complexes was prepared to investigate second and outer coordination sphere effects on CO2 hydrogenation catalysis, where X is CH2 (dppp) or X-R is N-CH3, N-CH2COOH (glycine), N-CH2COOCH3 (Gly-OMe), or N-CH2C(O)N-CH(CH3)-COOCH3 (GlyAla-OMe). All of these complexes were active for CO2 reduction to formate, with the N-CH3 derivative offering an 8-fold enhancement over the dppp derivative, which is consistent with increased electron density around the metal. Despite the increase in rate with the addition of the pendant nitrogen, the addition of electron withdrawing amino acids and dipeptides to the amine resulted in complexes with reductions in rate of 1 to 2 orders of magnitude, most consistent with a change in pK(a) of the pendant amine, resulting in lower activity. Collectively, the data suggest multiple contributions of the pendant amine in this catalytic system.