[bis(triphenylphosphoranylidene)ammonium][(nitrosyl)Fe(1,2-benzenedithiolato)2] | 608130-20-7

• 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: [bis(triphenylphosphoranylidene)ammonium][(nitrosyl)Fe(1,2-benzenedithiolato)2]
• 英文别名: [PPN][(ON)Fe(μ-S,S-1,2-benzenedithiolate)]；[PPN][(NO)Fe(S,S-C6H4)2]；[bis(triphenylphosphoranylidene)ammonium][(NO)Fe(S2C6H4)2]；[PPN][(ON)Fe(S,S-C6H4)2]；[PPN][(NO)Fe(S2C6H4)2]
• CAS: 608130-20-7
• 化学式: C₁₂H₈FeNOS₄*C₃₆H₃₀NP₂
• 分子量: 904.901
• InChiKey: UBCSEFSXVNBUTR-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：

  [bis(triphenylphosphoranylidene)ammonium][(nitrosyl)Fe(1,2-benzenedithiolato)2] 在 HBF₄ 作用下， 以 四氢呋喃 为溶剂， 以40%的产率得到[(ON)Fe(μ-S,S-C6H4)]3
  参考文献：
  名称：

  一类铁-硫醇盐-亚硝基化合物的新成员：含有 Fe3S6Core 的三核铁-硫醇盐-亚硝基配合物

  摘要：

  中性三核铁-硫醇盐-亚硝酰基 [(ON)Fe(mu-S,SC(6)H(4))](3) (1) 及其氧化产物 [(ON)Fe(mu-S) ,SC(6)H(4))](3)[PF(6)] (2)，通过 IR、X 射线衍射、X 射线吸收、电子顺磁共振 (EPR) 和磁共振进行合成和表征测量。当配合物 1 被氧化生成配合物 2 时，配合物 1 中每个铁原子周围的五配位四方锥体几何结构保持完整。磁测量和 EPR 结果表明配合物 1 中只有一个未配对电子（S(total) = 1 /2) 并且在 2 中没有未成对电子 (S(total) = 0)。复合物 1 和 2 之间的详细几何比较有助于理解未成对电子在该三核复合物的化学键合中所起的作用。Fe-Fe、Fe-N、当配合物 1 被氧化为 2 时，观察到 Fe(1) 周围的 Fe-S 距离和 Fe-S 距离。该结果表明未成对电子的去除确实诱导了 Fe-Fe、Fe-N

  DOI：

  10.1021/ja065401e
• 作为产物：
  描述：

  [bis(triphenylphosphoranylidene)ammonium][(nitrosyl)Fe(dithio-o-semibenzoquinone(1-) radical)(SC6H4SO2)] 在 三苯基膦 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 [bis(triphenylphosphoranylidene)ammonium][(nitrosyl)Fe(1,2-benzenedithiolato)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

文献信息

• Nitrosylated Iron−Thiolate−Sulfinate Complexes with {Fe(NO)}^6/7 Electronic Cores:  Relevance to the Transformation between the Active and Inactive NO-Bound Forms of Iron-Containing Nitrile Hydratases
  作者：Chien-Ming Lee、Chien-Hong Chen、Hao-Wen Chen、Jo-Lu Hsu、Gene-Hsiang Lee、Wen-Feng Liaw

  DOI：10.1021/ic050108l

  日期：2005.9.1

  complexes 7-9 with the less electron-donating sulfinate ligand coordinated to the Fe(NO)}7 core were oxidized by O2 to yield complexes 4-6. Obviously, the electronic perturbation of the Fe(NO)}7 core caused by the coordinated sulfinate in complexes 7-9 may serve to regulate the reactivity of complexes 7-9 toward O2. The iron-sulfinate nitrosyl species with the Fe(NO)}6/7 core exhibit the photolabilization

  五配位的硫醇铁亚硝酰基络合物[（NO）Fe（S，S-C6H3R）2]-（R = H（1），m-CH3（2）），[（NO）Fe（S，S- C6H2-3,6-Cl2）2]-（3），[（NO）Fe（S，S-C6H3R）2] 2-（R = H（10），m- （11））和[[ NO）Fe（S，S- -3,6-Cl2）2] 2-（12）已被分离并进行结构表征。O2触发含有Fe（NO）} 6核的硫醇铁亚硝基配合物1-3的硫氧合，生成S键合的单亚磺酸盐铁物种[（NO）Fe（S，SO2-C6H3R）（S，S -C6H3R）]-（R = H（4），m- （5））和[（NO）Fe（S，SO2- -3,6-Cl2）（S，S- -3,6- Cl2）] 2（2-）（6）。相反，O2对Fe（NO）} 7络合物10的攻击导致形成络合物1，并伴随有次要产物[Fe（S，S-C6H4）2] 2（2-）和[NO3]
• 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.
• Homodinuclear Iron Thiolate Nitrosyl Compounds [(ON)Fe(S,S-C₆H₄)₂Fe(NO)₂]^- and [(ON)Fe(SO₂,S-C₆H₄)(S,S-C₆H₄)Fe(NO)₂]^- with {Fe(NO)}⁷−{Fe(NO)₂}⁹ Electronic Coupling:  New Members of a Class of Dinitrosyl Iron Complexes
  作者：Hao-Wen Chen、Chin-Wei Lin、Chiao-Chun Chen、Li-Bo Yang、Ming-Hsi Chiang、Wen-Feng Liaw

  DOI：10.1021/ic049105j

  日期：2005.5.1

  Reaction of Fe(CO)(2)(NO)(2) and [(ON)Fe(S,S-C6H3R)(2)](-) (R = H (1), CH3 (1-Me))/[(ON)Fe(SO2,S-C6H4)(S,S-C6H4)](-) (4) in THF afforded the diiron thiolate/sulfinate nitrosyl complexes [(ON)Fe(S,S-C6H3R)(2)Fe(NO)(2)](-) (R = H (2), CH3 (2-Me)) and [(ON)Fe(S,SO2-C6H4)(S,S-C6H4)Fe(NO)(2)](-) (3), respectively. The average N-O bond lengths ([Fe(NO)(2)] unit) of 1.167(3) and 1.162(4) angstrom in complexes 2 and 3 are consistent with the average N-O bond length of 1.165 angstrom observed in the other structurally characterized dinitrosyl iron complexes with an Fe(NO)(2)}(9) core. The lower v((NO)-N-15) value (1682 cm(-1) (KBr)) of the [((NO)-N-15)FeS4] fragment of [((NO)-N-15)Fe(S,S-C6H3CH3)(2)Fe(NO)(2)](-) (2-Me-N-15), compared to that of [((NO)-N-15)Fe(S,S-C6H3CH3)(2)](-) (1-Me-N-15) (1727 cm(-1) (KBr)), implicates the electron transfer from Fe(NO)(2)}(10) Fe(CO)(2)(NO)(2) to complex 1-Me/1 may occur in the process of formation of complex 2-Me/2. Then, the electronic structures of the [(NO)FeS4] and [S2Fe(NO)(2)] cores of complexes 2, 2-Me, and 3 were best assigned according to the Feltham-Enemark notation as the Fe(NO)}(7)-Fe(NO)(2)}(9) coupling (antiferromagnetic interaction with a J value of -182 cm(-1) for complex 2) to account for the absence of paramagnetism (SQUID) and the EPR signal. On the basis of Fe-N(O) and N-O bond distances, the dinitrosyliron L2Fe(NO)(2)} derivatives having an Fe-N(O) distance of similar to 1.670 angstrom and a N-O distance of -1.165 angstrom are best assigned as Fe(NO)(2)}(9) electronic structures, whereas the Fe-N(O) distance of -1.650 angstrom and N-O distance of -1.190 angstrom probably imply an Fe(NO)(2)}(10) electronic structure.