[PPN][(C4H8O)Fe(S,S-C6H4)2] | 608130-18-3

• 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: [PPN][(C4H8O)Fe(S,S-C6H4)2]
• 英文别名: benzene-1,2-dithiolate;bis(triphenyl-λ5-phosphanylidene)azanium;iron(3+);oxolane
• CAS: 608130-18-3
• 化学式: C₁₆H₁₆FeOS₄*C₃₆H₃₀NP₂
• 分子量: 947.002
• InChiKey: SSQAYDRMFLWUGW-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  10.2
• 重原子数：
  61
• 可旋转键数：
  6
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  14.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  [PPN][(C4H8O)Fe(S,S-C6H4)2] 以 四氢呋喃 为溶剂， 生成 [bis(triphenylphosphoranylidene)ammonium][Fe(nitrosyl)2(S5)]
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1021/ic0494915
• 作为产物：
  描述：

  四氢呋喃 、 [PPN][Fe(CO)2(CN)(S,NH-C6H4)] 、 1,2-苯二硫醇 以 四氢呋喃 为溶剂， 以80%的产率得到[PPN][(C4H8O)Fe(S,S-C6H4)2]
  参考文献：
  名称：

  氧与亚硝基化铁-硫醇盐复合物中的硫结合：与含铁腈水合酶的相关性

  摘要：

  含有 S 键合的单亚磺酸盐 [PPN][(NO)Fe(S,SO2-C6H4)(S,S-C6H4)] (3) 的亚硝酰基铁配合物已从配合物 [PPN][(NO) 的硫氧化中分离出来Fe(S,S-C6H4)2] (2) 是在有机溶剂中通过将 NO 分子添加到 [PPN][(C4H8O)Fe(S,S-C6H4)2] (1) 中获得的。该结果表明，NO 与铁中心的结合促进了二硫醇铁被双氧的硫氧化并稳定了 S 键合的亚磺酸铁物质。对配合物 2 和 3 的键角分析表明，铁最好被描述为存在于扭曲的三角双锥配位环境中，该环境被配合物 3 中的一个 NO、三个硫醇盐和一个亚磺酸盐包围，而在配合物中采用扭曲的方形金字塔几何形状2. 配合物 3 在有机溶剂中与分子氧在 [PPN][NO2] 存在下进一步反应生成双核双（亚磺酸盐）配合物 [PPN]2[(NO)Fe(SO2,SO2-C6H4)(S,S- C6H4)]2

  DOI：

  10.1021/ja035292t