Ethyl 2-[3-[4-[5-[4-[3-[(2-ethoxy-2-oxoethyl)amino]-3-oxopropyl]phenyl]-3,7-diphenyl-1,5,3,7-diazadiphosphocan-1-yl]phenyl]propanoylamino]acetate | 1292323-26-2

• 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: Ethyl 2-[3-[4-[5-[4-[3-[(2-ethoxy-2-oxoethyl)amino]-3-oxopropyl]phenyl]-3,7-diphenyl-1,5,3,7-diazadiphosphocan-1-yl]phenyl]propanoylamino]acetate
• 英文别名: ethyl 2-[3-[4-[5-[4-[3-[(2-ethoxy-2-oxoethyl)amino]-3-oxopropyl]phenyl]-3,7-diphenyl-1,5,3,7-diazadiphosphocan-1-yl]phenyl]propanoylamino]acetate
• CAS: 1292323-26-2
• 化学式: C₄₂H₅₀N₄O₆P₂
• 分子量: 768.83
• InChiKey: LRPXJQWTMFMMMR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  54
• 可旋转键数：
  18
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  117
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  hexakis(acetonitrile)nickel(II) tetrafluoroborate 、 Ethyl 2-[3-[4-[5-[4-[3-[(2-ethoxy-2-oxoethyl)amino]-3-oxopropyl]phenyl]-3,7-diphenyl-1,5,3,7-diazadiphosphocan-1-yl]phenyl]propanoylamino]acetate 以 乙腈 为溶剂， 以85%的产率得到
  参考文献：
  名称：

  Incorporating Peptides in the Outer-Coordination Sphere of Bioinspired Electrocatalysts for Hydrogen Production

  摘要：

  Four new cyclic 1,5-diaza-3,7-diphosphacyclooctane ligands have been prepared and used to synthesize [Ni(p(2)(ph)N(2)(R))(2)](2+) complexes in which R is a mono- or dipeptide. These complexes represent a first step in the development of an outer-coordination sphere for this class of complexes that can mimic the outer-coordination sphere of the active sites of hydrogenase enzymes. Importantly, these complexes retain the electrocatalytic activity of the parent [Ni((P2N2Ph)-N-Ph)(2)](2+) complex in an acetonitrile solution with turnover frequencies for hydrogen production ranging from 14 to 25 s(-1) in the presence of p-cyanoaniliniurn trifluoromethanesulfonate and from 135 to 1000 s(-1) in the presence of protonated dimethylformamide, with moderately low overpotentials, similar to 0.3 V. The addition of small amounts of water results in rate increases of 2-7 times. Unlike the parent complex, these complexes demonstrate dynamic structural transformations in solution. These results establish a building block from which larger peptide scaffolding can be added to allow the [Ni(p(2)(R)N(2)(R'))(2)](2+) molecular catalytic core to begin to mimic the multifunctional outer-coordination sphere of enzymes.

  DOI：

  10.1021/ic1025872
• 作为产物：
  描述：

  3-[4-[5-[4-(2-Carboxyethyl)phenyl]-3,7-diphenyl-1,5,3,7-diazadiphosphocan-1-yl]phenyl]propanoic acid 、 2-氨基乙酸乙酯,磷酸 在 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 作用下， 以 四氢呋喃 为溶剂， 反应 19.0h， 以82%的产率得到Ethyl 2-[3-[4-[5-[4-[3-[(2-ethoxy-2-oxoethyl)amino]-3-oxopropyl]phenyl]-3,7-diphenyl-1,5,3,7-diazadiphosphocan-1-yl]phenyl]propanoylamino]acetate
  参考文献：
  名称：

  Incorporating Peptides in the Outer-Coordination Sphere of Bioinspired Electrocatalysts for Hydrogen Production

  摘要：

  Four new cyclic 1,5-diaza-3,7-diphosphacyclooctane ligands have been prepared and used to synthesize [Ni(p(2)(ph)N(2)(R))(2)](2+) complexes in which R is a mono- or dipeptide. These complexes represent a first step in the development of an outer-coordination sphere for this class of complexes that can mimic the outer-coordination sphere of the active sites of hydrogenase enzymes. Importantly, these complexes retain the electrocatalytic activity of the parent [Ni((P2N2Ph)-N-Ph)(2)](2+) complex in an acetonitrile solution with turnover frequencies for hydrogen production ranging from 14 to 25 s(-1) in the presence of p-cyanoaniliniurn trifluoromethanesulfonate and from 135 to 1000 s(-1) in the presence of protonated dimethylformamide, with moderately low overpotentials, similar to 0.3 V. The addition of small amounts of water results in rate increases of 2-7 times. Unlike the parent complex, these complexes demonstrate dynamic structural transformations in solution. These results establish a building block from which larger peptide scaffolding can be added to allow the [Ni(p(2)(R)N(2)(R'))(2)](2+) molecular catalytic core to begin to mimic the multifunctional outer-coordination sphere of enzymes.

  DOI：

  10.1021/ic1025872

文献信息

• Electrocatalytic Oxidation of Formate with Nickel Diphosphine Dipeptide Complexes: Effect of Ligands Modified with Amino Acids
  作者：Brandon R. Galan、Matthew L. Reback、Avijita Jain、Aaron M. Appel、Wendy J. Shaw

  DOI：10.1002/ejic.201300751

  日期：2013.10.14

  A series of nickel bis-diphosphine complexes with dipeptides appended to the ligands were investigated for the catalytic oxidation of formate. Typical rates of ~7 s-1 were found, similar to the parent complex (~8 s-1), with amino acid size and positioning contributing very little to rate or operating potential. Hydroxyl functionalities did result in lower rates, which were recovered by protecting the

  研究了一系列带有附加到配体的二肽的镍双二膦配合物用于甲酸盐的催化氧化。发现了~7 s-1 的典型速率，类似于母体复合物（~8 s-1），氨基酸大小和定位对速率或操作潜力的贡献很小。羟基官能团确实导致较低的速率，这可以通过保护羟基来恢复。结果表明，由二肽引入的整体电介质在催化中没有发挥重要作用，但游离羟基确实影响活性，表明来自分子内或分子间相互作用的贡献。这些观察结果对于深入了解类酶外配位球对分子催化剂的影响非常重要。这项工作由美国能源部基础能源科学、化学科学、地球科学和生物科学部（BRG、AJ、AMA、WJS）、美国能源部基础能源科学、物理生物科学计划（MLR）资助。太平洋西北国家实验室由巴特尔为美国能源部运营。