meso-1,3,6-triphenyl-1-aza-3,6-diphosphacycloheptane | 1132094-39-3

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: meso-1,3,6-triphenyl-1-aza-3,6-diphosphacycloheptane
• 英文别名: 1-para-phenyl-3,6-diphenyl-1-aza-3,6-diphosphacycloheptane
• CAS: 1132094-39-3
• 化学式: C₂₂H₂₃NP₂
• 分子量: 363.379
• InChiKey: DVEGFASWAADIPZ-PLQXJYEYSA-N

物化性质

• 熔点：
  80-82 °C(Solv: ethanol (64-17-5))
• 沸点：
  533.7±49.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.04
• 重原子数：
  25.0
• 可旋转键数：
  3.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  3.24
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为产物：
  描述：

  1,2-bis[(hydroxymethyl)(phenyl)phosphino]ethane 、 苯胺 以 乙醇 为溶剂， 生成 meso-1,3,6-triphenyl-1-aza-3,6-diphosphacycloheptane 、 rac-1,3,6-triphenyl-1-aza-3,6-diphosphacycloheptane
  参考文献：
  名称：

  1,3,6-氮杂二磷酸环庚烷：一种新型杂环二膦

  摘要：

  新型七元环二膦，即 1,3,6-氮杂二磷环庚烷，是通过 1,2-双（苯基膦基）乙烷、甲醛和伯胺（苯胺、对甲苯胺、苄胺和5-氨基间苯二甲酸）作为外消旋和内消旋立体异构体的混合物。通过 X 射线晶体结构分析研究了 N-甲苯基和 N-(3',5'-二羧基苯基)-取代的二膦的外消旋立体异构体的结构。N-(3',5'-二羧基苯基)-取代化合物的立体异构体在制备规模上被分离，并获得了它们的二氯化铂(II)配合物。相应的内消旋异构体很容易与 [PtCl2(cod)] 形成 P,P-螯合物，而外消旋立体异构体则形成低聚复合物。© 2008 Wiley Periodicals, Inc. 杂原子化学 19:125–132, 2008; 在线发表于 Wiley InterScience (www.interscience.wiley.com)。DOI 10.1002/hc.20397

  DOI：

  10.1002/hc.20397

文献信息

• High Catalytic Rates for Hydrogen Production Using Nickel Electrocatalysts with Seven-Membered Cyclic Diphosphine Ligands Containing One Pendant Amine
  作者：Michael P. Stewart、Ming-Hsun Ho、Stefan Wiese、Mary Lou Lindstrom、Colleen E. Thogerson、Simone Raugei、R. Morris Bullock、Monte L. Helm

  DOI：10.1021/ja400181a

  日期：2013.4.24

  A series of Ni-based electrocatalysts, [Ni(7P(2)(Ph)N(C6H4X))(2)](BF4)(2), featuring seven-membered cyclic diphosphine ligands incorporating a single amine base, 1-para-X-phenyl-3,6-triphenyl-1-aza-3,6-diphosphacycloheptane (7P(2)(Ph)N(C6H4X), where X = OMe, Me, Br, Cl, or CF3), have been synthesized and characterized. X-ray diffraction studies have established that the [Ni(7P(2)(Ph)N(C6H4X))(2)](2+) complexes have a square planar geometry, with bonds to four phosphorus atoms of the two bidentate diphosphine ligands. Each of the complexes is an efficient electrocatalyst for hydrogen production at the potential of the Ni(II/I) couple, with turnover frequencies ranging from 2400 to 27 000 s(-1) with [(DMF)H](+) in acetonitrile. Addition of water (up to 1.0 M) accelerates the catalysis, giving turnover frequencies ranging from 4100 to 96 000 s(-1). Computational studies carried out on the [Ni(7P(2)(Ph)N(C6H4X))(2)](2+) family indicate the catalytic rates reach a maximum when the electron-donating character of X results in the pK(a) of the Ni(I) protonated pendant amine matching that of the acid used for proton delivery. Additionally, the fast catalytic rates for hydrogen production by the [Ni(7P(2)(Ph)NC(6H4X))(2)](2+) family relative to the analogous [Ni((P2N2C6H4X)-N-Ph)(2)](2+) family are attributed to preferred formation of endo protonated isomers with respect to the metal center in the former, which is essential to attain suitable proximity to the reduced metal center to generate H-2. The results of this work highlight the importance of precise pK(a) matching with the acid for proton delivery to obtain optimal rates of catalysis.