Ethyl 3-[4-[5-[4-(3-ethoxy-3-oxopropyl)phenyl]-3,7-diphenyl-1,5,3,7-diazadiphosphocan-1-yl]phenyl]propanoate | 1292323-25-1

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: Ethyl 3-[4-[5-[4-(3-ethoxy-3-oxopropyl)phenyl]-3,7-diphenyl-1,5,3,7-diazadiphosphocan-1-yl]phenyl]propanoate
• 英文别名: ethyl 3-[4-[5-[4-(3-ethoxy-3-oxopropyl)phenyl]-3,7-diphenyl-1,5,3,7-diazadiphosphocan-1-yl]phenyl]propanoate
• CAS: 1292323-25-1
• 化学式: C₃₈H₄₄N₂O₄P₂
• 分子量: 654.726
• InChiKey: YNMMWHKYAJRYSB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.5
• 重原子数：
  46
• 可旋转键数：
  14
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  59.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  hexakis(acetonitrile)nickel(II) tetrafluoroborate 、 Ethyl 3-[4-[5-[4-(3-ethoxy-3-oxopropyl)phenyl]-3,7-diphenyl-1,5,3,7-diazadiphosphocan-1-yl]phenyl]propanoate 以 乙腈 为溶剂， 以91%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-氨基苯基)丙酸乙酯 、 双(羟甲基)苯膦 以 乙醇 为溶剂， 以87%的产率得到Ethyl 3-[4-[5-[4-(3-ethoxy-3-oxopropyl)phenyl]-3,7-diphenyl-1,5,3,7-diazadiphosphocan-1-yl]phenyl]propanoate
  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

• The Role of a Dipeptide Outer-Coordination Sphere on H₂-Production Catalysts: Influence on Catalytic Rates and Electron Transfer
  作者：Matthew L. Reback、Bojana Ginovska-Pangovska、Ming-Hsun Ho、Avijita Jain、Thomas C. Squier、Simone Raugei、John A. S. Roberts、Wendy J. Shaw

  DOI：10.1002/chem.201202849

  日期：2013.2.4

  presence of an amide bond increases rates, suggesting a role for the amide in assisting catalysis. Overpotentials were lower with substituents at the N‐phenyl meta position. This is consistent with slower electron transfer in the less compact, para‐substituted complexes, as shown in digital simulations of catalyst cyclic voltammograms and computational modeling of the complexes. Combining the current

  酶的外部配位层可微调活性位点的反应性并控制催化速率，这表明将类似的结构元素掺入分子催化剂中可能是必需的，以达到与在低超电势下在酶系统中观察到的速率相当的速率。在这项工作中，我们评估了氨基酸和二肽外配位球对[Ni（P Ph 2 N Ph-R 2）2 ] 2+产氢催化剂的影响。制备了一系列包含非天然氨基酸或二肽的12种新配合物，以测试位置，大小，极性和芳香性对催化活性的影响。非天然氨基酸要么3-（间-或对氨基苯丙酸丙酸以酸，酯或酰胺终止。二肽由非天然氨基酸之一与四种氨基酸酯之一组成：丙氨酸，丝氨酸，苯丙氨酸或酪氨酸。所有催化剂都对产氢具有活性，平均速率约为1000 s -1，比未改性的催化剂快40％。C末端肽的脂族或芳族侧链的结构和极性不会强烈影响速率。然而，酰胺键的存在增加了速率，表明酰胺在辅助催化中的作用。在N-苯基间位带有取代基的超电势较低。这与较不紧凑，对等的电子传输较慢相一致。-取代
• Incorporating Peptides in the Outer-Coordination Sphere of Bioinspired Electrocatalysts for Hydrogen Production
  作者：Avijita Jain、Sheri Lense、John C. Linehan、Simone Raugei、Herman Cho、Daniel L. DuBois、Wendy J. Shaw

  DOI：10.1021/ic1025872

  日期：2011.5.2

  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.