Fe(NO)₂(cis-1,2-bis(diphenylphosphino)ethylene) | 133128-61-7

• 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: Fe(NO)₂(cis-1,2-bis(diphenylphosphino)ethylene)
• 英文别名: Fe(NO)₂(DPPEt)；Fe(nitrosyl)2(cis-1,2-bis(diphenylphosphino)ethylene)；Fe(NO)2(dppv)
• CAS: 133128-61-7；133128-63-9
• 化学式: C₂₆H₂₂FeN₂O₂P₂
• 分子量: 512.267
• InChiKey: CVQGJMUKXXLLDQ-FAIYXUOWSA-N

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

• 作为产物：
  描述：

  Fe(NO)₂(CO)(cis-1,2-bis(diphenylphosphino)ethylene) 反应 84.0h， 以0.353 g的产率得到Fe(NO)₂(cis-1,2-bis(diphenylphosphino)ethylene)
  参考文献：
  名称：

  A combined experimental and theoretical study of dinitrosyl iron complexes containing chelating bis(diphenyl)phosphinoX (X=benzene, propane and ethylene): X-ray crystal structures and properties influenced by the presence or absence of π-bonds in chelating ligands

  摘要：

  Recent discoveries involving the roles of nitric oxide in humans have stimulated intense interest in transition metal nitrosyl complexes. A series of dinitrosyl iron complexes with the formula [(DPPX)Fe(NO)(2)], (DPPX = 1,2-bis(diphenylphosphino)benzene (1), 1,3-bis(diphenylphosphino)propane (2), and cis-1,2-bis(diphenylphosphino)ethylene (3)) has been prepared and characterized through a combination of FT-IR, NMR, UV-Vis, X-ray crystallography, and electrochemical techniques. Infrared spectroscopy showed NO shifts to the region of 1723 and 1674 cm(-1) for complexes 1 and 3, and 1708 and 1660 cm(-1) for 2, indicating that ligand 2 acts as a stronger sigma-donor. The X-ray crystallographic data showed that 1 and 3 possess the rare repulso conformation while 2 has the attracto conformation. CV studies on compounds 1, 2 and 3 display two quasi-reversible oxidations with the E degrees(1/2) values at 0.101 and 0.186 V. 0.121 and 0.184 V. and 0.019 and 0.342 V, respectively. The larger triangle E value for compound 2 compared with that of 1 and 3 is attributed to the lack of n-bonds between the two phosphorus atoms. Theoretical calculations using density functional theory were carried out on the synthesized compounds and model compounds and the results are consistent with the experimental data. The calculated HOMO-LUMO gaps for compounds 1, 2 and 3 are 3.736, 4.060, and 3.669 eV, respectively, which supports the stronger back-donation for compound 2 than that of compounds 1 and 3. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2013.12.019

文献信息

• New Nitrosyl Derivatives of Diiron Dithiolates Related to the Active Site of the [FeFe]-Hydrogenases
  作者：Matthew T. Olsen、Aaron K. Justice、Frédéric Gloaguen、Thomas B. Rauchfuss、Scott R. Wilson

  DOI：10.1021/ic801542w

  日期：2008.12.15

  Nitrosyl derivatives of diiron dithiolato carbonyls have been prepared starting from the precursor Fe(2)(S(2)C(n)H(2n))(dppv)(CO)(4) (dppv = cis-1,2-bis(diphenylphosphinoethylene). These studies expand the range of substituted diiron(I) dithiolato carbonyl complexes. From [Fe(2)(S(2)C(2)H(4))(CO)(3)(dppv)(NO)]BF(4) ([1(CO)(3)]BF(4)), the following compounds were prepared: [1(CO)(2)(PMe(3))]BF(4), [1(CO)(dppv)]BF(4)

  当氰化物是亲核试剂时，亚硝酰基从 Fe(dppv) 位点迁移，产生 Fe(CN)(2)(NO) 衍生物。化合物 [1(CO)(3)]BF(4)、[1(CO)(2)(PMe(3))]BF(4) 和 [1(CO)(dppv)]BF(4) 是也可以通过将 NO(+) 添加到二、三和四取代的前体中来制备。在这些情况下，NO(+) 似乎形成一个初始的 36e(-) 加合物，其中包含终端 Fe-NO，然后是脱羰。通过向混合价 Fe(I)Fe(II) 衍生物中添加 NO 来制备几种配合物。二铁亚硝酰基配合物在温和电位下还原，在某些情况下与 CO 形成弱加合物。 1(CO)(dppv) 的 IR 和 EPR 光谱，由 [1(CO)(dppv)]BF(4) 的低温还原生成) 与 Co(C(5)Me(5))(2)，表明 SOMO 位于 FeNO 亚基上。亚硝酰基从 Fe(dppv) 位点迁移，产生 Fe(CN)(2)(NO)