1,5-(di(4-(thiophene-3-yl)phenyl)-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) | 1187444-39-8

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 1,5-(di(4-(thiophene-3-yl)phenyl)-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane)
• 英文别名: 3,7-Diphenyl-1,5-bis(4-thiophen-3-ylphenyl)-1,5,3,7-diazadiphosphocane；3,7-diphenyl-1,5-bis(4-thiophen-3-ylphenyl)-1,5,3,7-diazadiphosphocane
• CAS: 1187444-39-8
• 化学式: C₃₆H₃₂N₂P₂S₂
• 分子量: 618.743
• InChiKey: AYSBSIGEICJQEG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.2
• 重原子数：
  42
• 可旋转键数：
  6
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  63
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  hexakis(acetonitrile)nickel(II) tetrafluoroborate 、 1,5-(di(4-(thiophene-3-yl)phenyl)-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) 以 乙腈 为溶剂， 以80%的产率得到[Ni(1,5-(di(4-(thiophen-3-yl)phenyl)-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane)2NCMe][BF4]2
  参考文献：
  名称：

  [Ni(PPh2NAr2)2(NCMe)][BF4]2 as an electrocatalyst for H2 production: PPh2NAr2=1,5-(di(4-(thiophene-3-yl)phenyl)-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane)

  摘要：

  A new cyclic 1,5-diaza-3,7-diphosphacyclooctane ligand was prepared with phenyl substituents on phosphorus and (thiophene-3-yl) phenyl substituents on nitrogen. This ligand reacts with [Ni(CH3CN)(6)][BF4](2) to form the corresponding [Ni((P2N2Ar)-N-Ph)(2)(NCMe)][BF4](2) complex, 3, which is an active electrocatalyst for H-2 production. Kinetic studies indicate that the catalytic rate is first order in catalyst and second order in acid at low concentrations of acid, but at higher acid concentrations the catalytic rate becomes independent of acid concentration. The rate-determining step at high acid concentrations is attributed to the elimination of H-2 from a reduced Ni species. The modest overpotential of 280 mV and a turnover frequency of 56 s(-1) confirm that 3 is a relatively active catalyst for H-2 production in acetonitrile solutions. Oxidation of the pendant thiophene substituents of 3 results in the formation of films on glassy carbon electrode surfaces. However these films are not electroactive, and electrocatalysis of proton reduction is not observed with these modified electrodes. (C) 2009 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2009.04.010
• 作为产物：
  描述：

  4-(噻吩-3-基)苯胺 、 双(羟甲基)苯膦 以 乙腈 为溶剂， 反应 3.0h， 以88%的产率得到1,5-(di(4-(thiophene-3-yl)phenyl)-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane)
  参考文献：
  名称：

  [Ni(PPh2NAr2)2(NCMe)][BF4]2 as an electrocatalyst for H2 production: PPh2NAr2=1,5-(di(4-(thiophene-3-yl)phenyl)-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane)

  摘要：

  A new cyclic 1,5-diaza-3,7-diphosphacyclooctane ligand was prepared with phenyl substituents on phosphorus and (thiophene-3-yl) phenyl substituents on nitrogen. This ligand reacts with [Ni(CH3CN)(6)][BF4](2) to form the corresponding [Ni((P2N2Ar)-N-Ph)(2)(NCMe)][BF4](2) complex, 3, which is an active electrocatalyst for H-2 production. Kinetic studies indicate that the catalytic rate is first order in catalyst and second order in acid at low concentrations of acid, but at higher acid concentrations the catalytic rate becomes independent of acid concentration. The rate-determining step at high acid concentrations is attributed to the elimination of H-2 from a reduced Ni species. The modest overpotential of 280 mV and a turnover frequency of 56 s(-1) confirm that 3 is a relatively active catalyst for H-2 production in acetonitrile solutions. Oxidation of the pendant thiophene substituents of 3 results in the formation of films on glassy carbon electrode surfaces. However these films are not electroactive, and electrocatalysis of proton reduction is not observed with these modified electrodes. (C) 2009 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2009.04.010

文献信息

• [Ni(PPh2NAr2)2(NCMe)][BF4]2 as an electrocatalyst for H2 production: PPh2NAr2=1,5-(di(4-(thiophene-3-yl)phenyl)-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane)
  作者：Douglas H. Pool、Daniel L. DuBois

  DOI：10.1016/j.jorganchem.2009.04.010

  日期：2009.8

  A new cyclic 1,5-diaza-3,7-diphosphacyclooctane ligand was prepared with phenyl substituents on phosphorus and (thiophene-3-yl) phenyl substituents on nitrogen. This ligand reacts with [Ni(CH3CN)(6)][BF4](2) to form the corresponding [Ni((P2N2Ar)-N-Ph)(2)(NCMe)][BF4](2) complex, 3, which is an active electrocatalyst for H-2 production. Kinetic studies indicate that the catalytic rate is first order in catalyst and second order in acid at low concentrations of acid, but at higher acid concentrations the catalytic rate becomes independent of acid concentration. The rate-determining step at high acid concentrations is attributed to the elimination of H-2 from a reduced Ni species. The modest overpotential of 280 mV and a turnover frequency of 56 s(-1) confirm that 3 is a relatively active catalyst for H-2 production in acetonitrile solutions. Oxidation of the pendant thiophene substituents of 3 results in the formation of films on glassy carbon electrode surfaces. However these films are not electroactive, and electrocatalysis of proton reduction is not observed with these modified electrodes. (C) 2009 Elsevier B.V. All rights reserved.