3-[4-[5-[4-(2-Carboxyethyl)phenyl]-3,7-diphenyl-1,5,3,7-diazadiphosphocan-1-yl]phenyl]propanoic acid | 1206734-23-7

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 苯丙酸
• 英文名称: 3-[4-[5-[4-(2-Carboxyethyl)phenyl]-3,7-diphenyl-1,5,3,7-diazadiphosphocan-1-yl]phenyl]propanoic acid
• 英文别名: 3-[4-[5-[4-(2-carboxyethyl)phenyl]-3,7-diphenyl-1,5,3,7-diazadiphosphocan-1-yl]phenyl]propanoic acid
• CAS: 1206734-23-7
• 化学式: C₃₄H₃₆N₂O₄P₂
• 分子量: 598.618
• InChiKey: CBOVHLCXMBPCMA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 重原子数：
  42
• 可旋转键数：
  10
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  81.1
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  3-[4-[5-[4-(2-Carboxyethyl)phenyl]-3,7-diphenyl-1,5,3,7-diazadiphosphocan-1-yl]phenyl]propanoic acid 在 1-羟基苯并三唑 、 O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate 、 N,N-二异丙基乙胺 、 氯化铵 作用下， 以 二氯甲烷 为溶剂， 反应 0.33h， 以82%的产率得到3,3'-((3,7-diphenyl-1,5,3,7-diazadiphosphocane-1,5-diyl)bis(4,1-phenylene))dipropanamide
  参考文献：
  名称：

  二肽外配位球在产氢催化剂上的作用：对催化速率和电子转移的影响

  摘要：

  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

  DOI：

  10.1002/chem.201202849
• 作为产物：
  描述：

  3-(4-氨基苯基)丙酸 、 双(羟甲基)苯膦 以 乙醇 为溶剂， 反应 16.0h， 以85%的产率得到3-[4-[5-[4-(2-Carboxyethyl)phenyl]-3,7-diphenyl-1,5,3,7-diazadiphosphocan-1-yl]phenyl]propanoic acid
  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

• Electric‐Field‐Mediated Electron Tunneling of Supramolecular Naphthalimide Nanostructures for Biomimetic H ₂ Production
  作者：Huan Lin、Zhiyun Ma、Jiwu Zhao、Yang Liu、Jinquan Chen、Junhui Wang、Kaifeng Wu、Huaping Jia、Xuming Zhang、Xinhua Cao、Xuxu Wang、Xianzhi Fu、Jinlin Long

  DOI：10.1002/anie.202009267

  日期：2021.1.18

  opposite‐charged DuBois‐Ni catalysts. The hot electrons of photoexcited BENI‐COO− nanofibers were tunneled to the molecular Ni collectors across a salt bridge and an alkyl region of 2.2–2.5 nm length at a rate of 6.10×108 s−1, which is five times larger than the BENI‐NH3+ nanoribbons (1.17×108 s−1). The electric field benefited significantly the electron tunneling dynamics and compensated the charge‐separated

  两个半导体双（4-乙炔基-桥接-1,8-萘二甲酰亚胺）bolaamphiphiles（BENI-COO的设计和合成-和贝尼-NH 3 +）制造超分子金属-绝缘体-半导体（MIS）的纳米结构为下仿生析氢可见光照射。大约AH 2的进化速率。3.12毫摩尔克-1 ⋅h -1和约的表观量子效率（AQE）在400nm处1.63％经达到BENI-COO - -NH 3 + -Ni MIS通过静电自组装BENI-COO的制备光系统-具有相反电荷的迪布瓦-Ni系催化剂。光激发的BENI-COO的热电子−纳米纤维通过盐桥和长度为2.2–2.5 nm的烷基区域以6.10×10 8  s -1的速率隧穿到分子Ni捕集剂，比BENI‐NH 3 +纳米带（1.17大五倍）×10 8  s -1）。电场显著受益的电子隧道效应动力学和补偿在BENI-COO不足电荷分离状态-纳米纤维。
• 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。
• A Hydrogen-Evolving Ni(P₂N₂)₂ Electrocatalyst Covalently Attached to a Glassy Carbon Electrode: Preparation, Characterization, and Catalysis. Comparisons with the Homogeneous Analogue
  作者：Atanu K. Das、Mark H. Engelhard、R. Morris Bullock、John A. S. Roberts

  DOI：10.1021/ic500701a

  日期：2014.7.7

  A hydrogen-evolving homogeneous Ni(P2N2)2 electrocatalyst with peripheral ester groups has been covalently attached to a 1,2,3-triazolyllithium-terminated planar glassy carbon electrode surface. Coupling proceeds with both the Ni(0) and the Ni(II) complexes. X-ray photoemission spectra show excellent agreement between the Ni(0) coupling product and its parent complex, and voltammetry of the surface-confined

  具有外围酯基的放氢均相Ni（P 2 N 2）2电催化剂已共价连接至以1,2,3-三唑基锂为末端的平面玻璃碳电极表面。Ni（0）和Ni（II）配合物都进行偶联。X射线光发射光谱表明Ni（0）偶联产物与其母体之间有极好的一致性，表面受限系统的伏安法表明，单一物质占优势，表面密度为1.3×10 –10 mol cm –2，接近密集包装的单层的估算值。使用Ni（II）系统时，光发射和伏安数据均显示出偶合时未鉴定产物的形态，其表面密度为6.7×10 –11 mol cm –2。表面受限的Ni（0）络合物是析氢的电催化剂，显示出与可溶母体络合物处于相同电位的催化电流的开始。在酸性乙腈中观察到了表面受限物质的分解。这被解释为反映了Ni（II）-膦相互作用的不稳定性和游离膦的碱性，并且还涉及同时实施表面受限的Ni（P 2 N 2）2的努力。 电化学或光电化学装置中的配合物。
• 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.