[bis(triphenylphosphoranylidene)ammonium][Fe(nitrosyl)2(S5)] | 748781-52-4

• 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: [bis(triphenylphosphoranylidene)ammonium][Fe(nitrosyl)2(S5)]
• 英文别名: [bis(triphenylphosphoranylidene)ammonium][S5Fe(NO)2]；[bis(triphenylphosphoranylidene)][Fe(S5)(NO)2]；[PNP][Fe(NO)2(S5)]；[PPN][Fe(S5)(NO)2]；[PPN][S5Fe(NO)2]
• CAS: 748781-52-4
• 化学式: C₃₆H₃₀NP₂*FeN₂O₂S₅
• 分子量: 814.778
• InChiKey: ACMRSJCDCMNNFG-UHFFFAOYSA-L

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：

  [bis(triphenylphosphoranylidene)ammonium][Fe(nitrosyl)2(S5)] 在 三苯基膦 作用下， 以 氘代苯 为溶剂， 反应 0.25h， 生成 [PPN]2[(NO)2Fe(μ-S)2Fe(NO)2]
  参考文献：
  名称：

  亚硫硝酸盐 (SNO−) 和过硫亚硝酸盐 (SSNO−) 是亚硝基化铁硫簇的简单合成子

  摘要：

  简单的 Fe 2+离子，例如那些在不稳定铁池中具有生物可利用性的离子，与亚硫硝酸盐 (SNO - ) 和过硫亚硝酸盐 (SSNO - ) 反应，产生与生物相关的 Fe−S 簇的合成子。

  DOI：

  10.1002/anie.202204570
• 作为产物：
  描述：

  [PPN][SC6H5-o-MHCOCH3] 以 四氢呋喃 、 乙腈 为溶剂， 生成 [bis(triphenylphosphoranylidene)ammonium][Fe(nitrosyl)2(S5)]
  参考文献：
  名称：

  二亚硝基铁络合物（DNIC）[L（2）Fe（NO）2]-（L =硫醇盐）：{Fe（NO）2} 9个DNIC，{Fe（NO）2} 10个DNIC和[2Fe- 2S]簇，以及硫醇盐配体在调节DNIC释放NO方面的关键作用。

  摘要：

  二亚硝基铁络合物[（-SC（7）H（4）SN）（2）Fe（NO）（2）]（-）（1）是通过[S（5）Fe（NO）（2）反应制备的]（-）和二（2-苯并噻唑基）二硫化物。在合成类似的二亚硝酰基铁化合物（DNIC）中，较强的供电子硫醇盐[RS]（-）（R = C（6）H（4）-o-NHCOCH（3），C（4）H（3 ）S，C（6）H（4）NH（2），Ph），与复合物1的[-SC（7）H（4）SN]（-）相比，触发硫醇盐-配体取代，产生[（- SC（6）H（4）-o-NHCOCH（3）（2）Fe（NO）（2）]（-）（2），[（-SC（4）H（3）S）（2） Fe（NO）（2）]（-）（3）和[（SPh）（2）Fe（NO）（2）]（-）（4）。在298 K时，配合物2和3在DNIC的特征g值分别为g = 2.038和2.027时显示出良好分辨的五线EPR信号。磁化率拟合表明2中的{Fe（+）（（

  DOI：

  10.1021/ic0505044

文献信息

• Roles of the Distinct Electronic Structures of the {Fe(NO)₂}⁹ and {Fe(NO)₂}¹⁰ Dinitrosyliron Complexes in Modulating Nitrite Binding Modes and Nitrite Activation Pathways
  作者：Fu-Te Tsai、Pei-Lin Chen、Wen-Feng Liaw

  DOI：10.1021/ja100849r

  日期：2010.4.14

  abstraction of the chelating nitrito ligand of the Fe(NO)(2)}(9) DNIC [(1-MeIm)(2)(eta(2)-ONO)Fe(NO)(2)] (5; 1-MeIm = 1-methylimidazole) to generate the Fe(NO)(2)}(10) DNIC [(1-MeIm)(PPh(3))Fe(NO)(2)] (6), glacial acetic acid protonation of the N-bound nitro ligand in the Fe(NO)(2)}(10) DNIC [PPN][(eta(1)-NO(2))(PPh(3))Fe(NO)(2)] (7) produced the Fe(NO)(2)}(9) DNIC [PPN][(OAc)(2)Fe(NO)(2)] (8), nitric

  [PPN](2)[(ONO)(2)Fe(eta(2)-ONO)(2)] [1; PPN = 双(三苯基亚膦基)铵] 产生含亚硝酸盐的 Fe(NO)}(7) 单亚硝基化合物 (MNIC) [PPN](2)[(NO)Fe(ONO)(3)(eta(2)- ONO)] (2). 在 4 K 时，配合物 2 表现出 S = (3)/(2) 轴向 EPR 谱，主 g 值为 g（垂直）= 3.971 和 g（平行）= 2.000，暗示 Fe(III)(NO( -))}(7) 电子结构。将 1 当量的 PPh(3) 添加到复合物 2 中会在温和条件下触发螯合亚硝基配体的 O 原子转移，从而产生 Fe(NO)(2)}(9) 二亚硝基甲酰亚基复合物 (DNIC) [PPN][( ONO)(2)Fe(NO)(2)] (3)。这些结果表明电子结构 [Fe(III)(NO(-))}(7), S = (3)/(2)]
• Dinitrosyl iron complexes [E5Fe(NO)2]− (E=S, Se): A precursor of Roussin’s black salt [Fe4E3(NO)7]−
  作者：Tai-Nan Chen、Feng-Chun Lo、Ming-Li Tsai、Ko-Nien Shih、Ming-Hsi Chiang、Gene-Hsiang Lee、Wen-Feng Liaw

  DOI：10.1016/j.ica.2006.02.035

  日期：2006.5

  [PPN][Se5Fe(NO)(2)] (1) and [K-18-crown-6-ether][S5Fe(NO)(2)] (2') were synthesized and characterized by IR, UV-Vis, EPR spectroscopy, magnetic susceptibility, and X-ray structure. [PPN][Se5Fe(NO)21 easily undergoes ligand exchange with S-8 and (RS)(2) (R = C7H4SN (5), o-C6H4NHCOCH3 (6), C4H3S (7)) to form [PPN][S5Fe(NO)(2)] and [PPN][(SR)(2)Fe(NO)(2)]. The reaction displays that [E5Fe(NO)(2)](-) (E = Se (3), S (4)) facilely converts to [Fe4E3(NO)(7)](-) by adding acid HBF4 or oxidant [Cp2Fe][BF4] in THF, respectively. Obviously, complexes 1 and 2' serve as the precursors of the Roussin's black salts 3 and 4. The electronic structure of Fe(NO)2)9 core of [Se5Fe(NO)(2)](-) is best described as a dynamic resonance hybrid of Fe+1(-NO)(2)}(9) and Fe-1(NO+)(2)}(9) modulated by the coordinated ligands. The findings, EPR signal of g = 2.064 for 1 at 298 K, implicate that the low-molecular-weight DNICs and protein-bound DNICs may not exist with selenocysteine residues of proteins as ligands, since the existence of protein-bound DNICs and low-molecular-weight DNICs in vitro has been characterized with a characteristic EPR signal at g = 2.03. In addition, complex 2' treated human erythroleukemia K562 cancer cells exposed to UV-A light greatly decreased the percentage survival of the cell cultures. (c) 2006 Elsevier B.V. All rights reserved.
• Photochemistry of the Dinitrosyl Iron Complex [S₅Fe(NO)₂]^- Leading to Reversible Formation of [S₅Fe(μ-S)₂FeS₅]²^-:  Spectroscopic Characterization of Species Relevant to the Nitric Oxide Modification and Repair of [2Fe−2S] Ferredoxins
  作者：Ming-Li Tsai、Chiao-Chun Chen、I-Jui Hsu、Shyue-Chu Ke、Chung-Hung Hsieh、Kuo-An Chiang、Gene-Hsiang Lee、Yu Wang、Jin-Ming Chen、Jyh-Fu Lee、Wen-Feng Liaw

  DOI：10.1021/ic0494915

  日期：2004.8.1

  The reaction of [PPN][Fe(CO)(3)(NO)] and S-8 in a 1:1 molar ratio in THF proceeded to give the dinitrosyl iron complex [PPN][S5Fe(NO)(2)] (1) and the known [PPN](2)[S5Fe(mu-S)(2)FeS5] (2). EPR signals of g values g(z) = 2.0148, g(x) = 2.0270, and g(y) = 2.0485 at 77 K confirmed the existence of the unpaired electron in compound 1. The temperature-dependent magnetic moment of complex 1 indicates that the ground state is one unpaired electron with (S-t, S-L) = (1/2, 1) at very low temperature (S-t is the total spin quantum number of the system; S-L is the sum of the spin quantum numbers of two NO ligands). The O K-edge absorptions of complex 1 and [(NO)Fe(S2CNEt2)(2)] at 532.1 and 532.5 eV are assigned to the transition of 1s --> pi*(NO) and 1s - pi*(NO+), respectively. For the electronic structure of the Fe(NO)(2)} core, DFT calculations, magnetic susceptibility measurement, EPR, and Fe K-/L-edge XAS spectroscopy of complex 1 lead to a description of Fe1+((NO)-N-.)(2)}(9). [2Fe-2S] cluster 2 treated with nitric oxide in THF shows that cluster 2 is transformed into the dinitrosyl iron complex 1 identified by IR, UV-vis, and X-ray diffraction analysis. The reaction may be reversed by the photolysis of the THF solution of 1 in the presence of the NO-accepting reagent [(C4H8O)Fe(S,S-C6H4)(2)](-) to reform 2. This result demonstrates a successful biomimetic reaction cycle of the degradation and reassembly of [2Fe-2S] cluster [S5Fe(mu-S)(2)FeS5](2-) relevant to the repair of nitric oxide-modified [2Fe-2S] ferredoxin by cysteine desulfurase and L-cysteine in vitro.