(Et4N)[(Cl2PhPepS)Fe(NO)(N,N-dimethyl-4-aminopyridine)] | 1160943-94-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (Et4N)[(Cl2PhPepS)Fe(NO)(N,N-dimethyl-4-aminopyridine)]
• 英文别名: [Et4N][Cl2PhPepS)Fe(nitrosyl)(DMAP)]；(Et4N)[(Cl2PhPepS)Fe(NO)(DMAP)]
• CAS: 1160943-94-1
• 化学式: C₈H₂₀N*C₂₇H₂₀Cl₂FeN₅O₃S₂
• 分子量: 783.626
• InChiKey: URXXIIMYYPNIEG-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  (Et4N)[(Cl2PhPepS)Fe(NO)(N,N-dimethyl-4-aminopyridine)] 以 乙腈 为溶剂， 生成 (Et4N)[(Cl2PhPepS)Fe(N,N-dimethyl-4-aminopyridine)]
  参考文献：
  名称：

  Rose, Michael J.; Betterley, Nolan M.; Mascharak, Pradip K., Journal of the American Chemical Society, 2009, vol. 131, p. 8340 - 8341

  摘要：

  DOI：
• 作为产物：
  描述：

  (Et4N)[(Cl2PhPepS)Fe(N,N-dimethyl-4-aminopyridine)] 在 [(PaPy₃)Mn(NO)]ClO₄ 作用下， 以 乙腈 为溶剂， 生成 (Et4N)[(Cl2PhPepS)Fe(NO)(N,N-dimethyl-4-aminopyridine)]
  参考文献：
  名称：

  Binding of Nitric Oxide to a Synthetic Model of Iron-Containing Nitrile Hydratase (Fe-NHase) and Its Photorelease: Relevance to Photoregulation of Fe-NHase by NO

  摘要：

  The activity of the non-heme iron enzyme nitrile hydratase (Fe-NHase) is modulated by nitric oxide (NO). The inactive (dark form) NO-bound enzyme is activated when exposed to light via the release of NO from the iron center. In order to determine whether oxygenation of active site Fe-bound Cys-S centers are involved in this process of NO regulation, a model complex (Et4N)[(Cl(2)PhPepS)Fe(NO)(DMAP)] (8) has been synthesized and structurally characterized. Complex 8 does not exhibit any NO photolability. However, following oxygenation of the Fe-bound thiolato-S centers to sulfinates (with the aid of oxaziridine), the resulting complex (Et4N)[(Cl(2)PhPep{SO2}(2))-Fe(NO)(DMAP)] (9) releases NO readily upon illumination with visible light. Spectroscopic properties of 8 and 9 confirm that these species do mimic the active site of Fe-NHase closely, and the results indicate that NO photolability is related to S-oxygenation. Results of density functional theory and time-dependent DFT studies on both 8 and 9 indicate that S-oxygenation weakens Fe-S bonding and that strong transitions near 470 nm transfer an electron from a carboxamido-N/sulfinato-SO2 MO to a d pi(Fe)-pi*(NO)/d(z)2(Fe)-sigma*(NO) antibonding orbital in 9. In case of 8, strong S-Fe-NO bonding interactions prevent the release of NO upon illumination. Together, the results of this work strongly suggest that oxygenated Cys-S centers play an important role in the process of NO regulation of Fe-NHases.

  DOI：

  10.1021/ic902220a