(Bu4N)2[Fe4S4(1,3,5-tris-((4,6-dimethyl-3-mercaptophenyl)thio)-2,4,6-tris-(p-tolylthio)benzenate(3-))(SC2H5)] | 137003-15-7

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: (Bu4N)2[Fe4S4(1,3,5-tris-((4,6-dimethyl-3-mercaptophenyl)thio)-2,4,6-tris-(p-tolylthio)benzenate(3-))(SC2H5)]
• 英文别名: (Bu4N)2{Fe4S4(1,3,5-tris((4,6-dimethyl-3-mercapto-phenyl)thio)-2,4,6-tris(p-tolylthio)benzene)(SEt5)}；(N(C4H9)4)2[(1,3,5-tris(4,6-dimethyl-3-mercaptophenylthio)-2,4,6-tris(p-tolyl-thio)benzene)Fe4S4(SC2H5)]；[Bu4N]2[Fe4S4(1,3,5-tris((4,6-dimethyl-3-mercaptophenyl)thio)-2,4,6-tris(p-tolylthio)benzene(3-))(SEt)]；[Bu4N]2[Fe4S4(LS3)(SEt)]
• CAS: 137003-15-7
• 化学式: 2C₁₆H₃₆N*C₅₃H₅₀Fe₄S₁₄
• 分子量: 1844.23
• InChiKey: ZNKKPYAHKZRGLH-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  27.83
• 重原子数：
  88.0
• 可旋转键数：
  20.0
• 环数：
  17.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  10.0

反应信息

• 作为反应物：
  描述：

  (Bu4N)2[Fe4S4(1,3,5-tris-((4,6-dimethyl-3-mercaptophenyl)thio)-2,4,6-tris-(p-tolylthio)benzenate(3-))(SC2H5)] 在 H₂S 作用下， 以 吡啶 为溶剂， 以86%的产率得到
  参考文献：
  名称：

  Synthesis and Electron Delocalization of [Fe4S4]-S-Fe(III) Bridged Assemblies Related to the Exchange-Coupled Catalytic Site of Sulfite Reductases

  摘要：

  Because of the pervasive occurrence of magnetically coupled siroheme and Fe4S4 units in assimilatory and dissimilatory sulfite and nitrite reductases, we have undertaken the synthesis of the sulfide-bridged assembly Fe4S4-S-heme as a possible analogue to the active sites of certain assimilatory enzymes. The approach has utilized iron subsite-differentiated clusters of the type [Fe4S4(LS(3))L'](2-), which undergo regiospecific substitution at the unique subsite. Reaction of [Fe4S4(LS(3))(SEt)](2-) with limited H2S in acetonitrile affords the functionalized cluster [Fe4S4(LS(3))(SH)](2-) (4), which exists in equilibrium with the mu-S double cubane {[Fe4S4(LS(3))]S-2}(4-) (6) and H2S. Reaction of 4 and [Fe(salen)]O-2 gave the bridged assembly [Fe4S4(LS(3))-S-Fe-III(salen)](2-) (8), detectable by its characteristic isotropically shifted H-1 NMR spectrum. Six routes were devised to a related heme-based assembly: directed acid-base coupling of 4 with [Fe(OEP)]O-2, [Fe(OEP)(OMe)], [Fe(OEP)(OC(Me)=CH2)], and [Fe(OEP)(OClO3)]/Et(3)N; Si-S bond cleavage in the reaction of [Fe4S4(LS(3))(SSiEt(3))](2-) with [Fe(OEP)F]; oxidative addition of [Fe-II(OEP)] to the disulfide bond of the mu-S-2 double cubane {[Fe4S4(LS(3))]S-2(2)}(4-) (7). In each case, the product was [Fe4S4(LS(3))-S-Fe-III(OEP)](2-) (9), recognizable by UV-visible absorption and H-1 NMR spectra. Both 8 and 9 contain [Fe4S4](2+) and high-spin Fe(III) fragments. Isotropic shifts mainly contact in origin that are enhanced by factors of 7-12 compared to those of precursor cluster 4, and the Curie-type temperature dependence of the shifts of 9, originate from extensive spin localization from the Fe(III) fragment to the cluster. This effect requires the existence of a covalent bridge between the fragments and, together with the methods of synthesis and other spectroscopic observations, provides structure proof of the bridged assemblies. These species sustain two one-electron reduction reactions; other reactions of 9, which alter or cleave the bridge, are summarized. The electronic features of bridged assemblies such as 8 and 9 approach the intrinsic magnetic and spectroscopic properties of a structurally similar unit in the oxidized enzymes and potentially provide a means of identification of such units. (LS(3) = 1,3,5-tris[(4,6-dimethyl-3-mercaptophenyl)-thio]-2,4,6-tris(p-tolylthio)benzene(3-); OEP octaethylporphyrinate(2-); salen = 1,2-bis(salicylidenearnino)ethane-(2-).)

  DOI：

  10.1021/ja00095a021
• 作为产物：
  描述：

  (Bu4N)2{Fe4S4(SEt)4} 、 1,3,5-tris((4,6-dimethyl-3-mercaptophenyl)thio)-2,4,6-tris(p-tolylthio)benzene 以 二氯甲烷 、 乙腈 为溶剂， 以85%的产率得到(Bu4N)2[Fe4S4(1,3,5-tris-((4,6-dimethyl-3-mercaptophenyl)thio)-2,4,6-tris-(p-tolylthio)benzenate(3-))(SC2H5)]
  参考文献：
  名称：

  Liu, Hong Ye; Scharbert, Bernd; Holm, Journal of the American Chemical Society, 1991, vol. 113, # 25, p. 9529 - 9539

  摘要：

  DOI：

文献信息

• Metal Ion Incorporation Reactions of the Cluster [Fe₃S₄(LS₃)]³^-, Containing the Cuboidal [Fe₃S₄]⁰ Core
  作者：Jian Zhou、James W. Raebiger、Charles A. Crawford、R. H. Holm

  DOI：10.1021/ja9704186

  日期：1997.7.1

  has prompted extensive investigation of its chemical and biological properties. The biological function remains in question, but the cluster is known to sustain two reactions: (i) electron transfer, and (ii) heterometal ion incorporation. The recent preparation of [Fe3S4(LS3)]3- (3) [Zhou, J.; Hu, Z.; Munck, E.; Holm, R. H. J. Am. Chem. Soc. 1996, 118, 1966] has permitted detailed structural, electronic

  立方体簇[Fe3S4(S·Cys)3]在多种蛋白质中的频繁出现促使对其化学和生物学特性的广泛研究。生物功能仍然存在问题，但已知该簇可维持两种反应：（i）电子转移和（ii）异金属离子掺入。[Fe3S4(LS3)]3-(3)[Zhou, J.; 胡志；蒙克，E。霍尔姆，RHJ 上午。化学 社会。1996, 118, 1966] 允许对立方 [Fe3S4]0 氧化态 (LS3 = 1,3,5-tris((4,6-dimethyl-3-mercaptophenyl)thio)-进行详细的结构、电子和反应性表征2,4,6-tris(p-tolylthio)benzo(3−). 氧化还原特性 (i) 之前已经报道过：这里的反应类型 (ii) 导致了立方烷型 MFe3S4 簇的形成，已被研究。3 与 [M(PPh3)4]1+ 反应得到 [(Ph3P)MFe3S4(LS3)]2- (M = Cu (6),
• On [Fe₄S₄]²⁺−(μ₂-SR)−M^II Bridge Formation in the Synthesis of an A-Cluster Analogue of Carbon Monoxide Dehydrogenase/Acetylcoenzyme A Synthase
  作者：P. Venkateswara Rao、Sumit Bhaduri、Jianfeng Jiang、Daewon Hong、R. H. Holm

  DOI：10.1021/ja040222n

  日期：2005.2.1

  complexes and the 3:1 site-differentiated clusters [Fe(4)S(4)(LS(3))L'](2-) (L' = TfO(-) (14), SEt (15)). The system 14/[Ni(L(O)-S(2)N(2))}M(SCH(2)CH(2)PPh(2))](+) results in cleavage of the dinuclear complex and formation of [Ni(L(O)-S(2)N(2))}Fe(4)S(4)(LS(3))]- (18), in which the Ni(II) complex binds at the unique cluster site with formation of a Ni(mu(2)-SR)(2)Fe bridge rhomb. Cluster 18 and the related

  一氧化碳脱氢酶/乙酰辅酶合成酶 A 簇的合成类似物的构建，乙酰辅酶 A 形成的位点，需要作为最后一步形成无支持的 [Fe(4)S(4)]-(mu( 2)-SR)-Ni(II) 桥接到预先形成的簇。我们之前的结果（Rao, PV；Bhaduri, S.；Jiang, J.；Holm, RH Inorg. Chem. 2004, 43, 5833）和其他人的工作已经解决了与 A 簇相关的双核复合物的合成问题。本研究通过检查包含双核和单核 Ni(II) 配合物和 3:1 位点分化簇 [Fe(4)S(4)(LS(3))L'](2 -) (L' = TfO(-) (14), SEt (15))。系统 14/[Ni(L(O)-S(2)N(2))}M(SCH(2)CH(2)PPh(2))](+) 导致双核复合物的裂解和形成 [Ni(L(O)-S(2)N(2))}Fe(4)S(4)(LS(3))]- (18)，其中
• The Cuboidal Fe₃S₄ Cluster:  Synthesis, Stability, and Geometric and Electronic Structures in a Non-Protein Environment
  作者：Jian Zhou、Zhengguo Hu、Eckard Münck、R. H. Holm

  DOI：10.1021/ja9537843

  日期：1996.1.1

  [Fe4S4(LS3)(SEt)]2- with (Et3NH)(OTf) affords [Fe4S4(LS3)(OTf)]2-, whose unique site is activated toward terminal ligand substitution. Treatment with 1 equiv of (Et4N)2(Meida) affords [Fe4S4(LS3)(Meida)]3-, which is readily converted to [Fe3S4(LS3)]3- with 1−2 equiv of additional reactant. The trinuclear cluster is formed by abstraction of Fe2+ from a precursor cubane-type [Fe4S4]2+ core and complexation as [Fe(Meida)2]2-

  在具有核心单元 Fe2S2、Fe4S4 和 Fe3S4 的金属生物分子中的三个已知低核铁硫簇中，最后一个尚未在蛋白质环境之外以稳定形式获得。我们描述了 [ ]0 氧化态下此类簇的直接途径，并证明了与天然簇的有效立体化学和电子结构一致。该合成基于铁位点分化的簇。[ (LS3)(SEt)]2- 与 (Et3NH)(OTf) 的反应得到 [ (LS3)(OTf)]2-，其独特的位点被激活到末端配体取代。用 1 当量的 (Et4N)2(Meida) 处理得到 [ (LS3)(Meida)]3-，它很容易转化为 [ (LS3)]3- 和 1-2 当量的额外反应物。三核簇是通过从前体立方烷型 [ ]2+ 核中提取 Fe2+ 并络合为 [Fe(Meida)2]2- 形成的。从 [Fe4SE4(LS3)(SEt)]2- 开始的类似过程产生 [Fe3SE4(LS3)]3-。化合物
• The influence of net charge on the redox potentials of Fe4S4 cubane-type clusters in aprotic solvents
  作者：Chaoyin Zhou、James W. Raebiger、Brent M. Segal、R.H. Holm

  DOI：10.1016/s0020-1693(99)00593-9

  日期：2000.4

  Abstract The recent demonstration of the existence of the [Fe4S4]0 oxidation state in the iron protein of nitrogenase raises the issue of stabilization of reduced states of Fe4S4 clusters in proteins and synthetic compounds. In thiolate-ligated clusters, potentials of the redox couples [Fe4S4(SR)4]2−/3− have been shown to scale linearly with substituent (R) constants. In this work, the combined result

  摘要最近证明了固氮酶铁蛋白中[ ] 0氧化态的存在引发了蛋白质和合成化合物中Fe4S4团簇还原态的稳定化问题。在硫醇盐连接的簇中，氧化还原对[ （SR）4] 2- / 3-的电势已显示出与取代基（R）常数成线性比例关系。在这项工作中，已通过使用先前报告的具有R = p-C6H4NO2，C6F5的簇和具有R = CH2CH2NMe3 +，p-C6H4NR3 +和p-C6H4CH2NR3的新簇来检查对电位的感应和静电作用的组合结果+。（Bu4N）2 [ （SC6H4-p-NO2）4]的晶体结构显示出四方压缩的[ ] 2+核。描述了硫醇阳离子p-HSC6H4NR3 +和p-HSC6H4CH2NR3 +的盐的合成。[ （SR）4] 2+和[1：3]通过配体取代反应制备位点分化的物质[ （LS3）（SR）] 1-。在质子惰性溶剂中报告了17个簇的电位（
• Comparative Isotropic Shifts, Redox Potentials, and Ligand Binding Propensities of [1:3] Site-Differentiated Cubane-Type [Fe₄Q₄]²⁺ Clusters (Q = S, Se)
  作者：Chaoyin Zhou、R. H. Holm

  DOI：10.1021/ic970254u

  日期：1997.8.1

  The [1:3] site-differentiated cubane-type clusters [F2(4)Q(4)(LS3))Cl](2-)(Q=S,Se;LS3=1,3,5-tris((4,6-dimethyl-3-mercaptophenyl)thio)-2,4,6-tris(p-tolylthio)benzenate(3-)) undergo substitution reactions at the unique iron site with a variety of ligands including thiolates, phenolates, cyclic triamines and a trisulfide, imidazoles, and tertiary phosphines. Reactions are readily followed because of the extreme sensitivity of isotropically shifted resonances to the nature of ligand L' in the product dusters [Fe(4)Q(4)(LS3)L'](2-,-), Isotropic shifts and redox potentials are reported for over 40 clusters, including many cluster pairs differing only in the core chalcogenide atom. In this way, comparative properties of sulfide and selenide clusters can be elicited. It is shown that the larger isotropic shifts consistently observed for selenide clusters and dominantly contact in nature arise from larger magnetic susceptibilities, which indicate a lesser extent of antiferromagnetic coupling. It is further demonstrated that, without exception, redox potentials of selenide clusters are more positive than those of sulfide clusters, usually by 20-60 mV, at parity of ligation. The difference in potentials of ca. 300 mV between the [Fe4S4](2+,+) couples of [Fe4S4(LS3)(SEt)](2-) and [Fe4S4(LS3)(Im)](-) (Im=imidazole) clusters is the best available estimate of the intrinsic potential difference between protein-bound [Fe4S4(Cys-S)(4)] and [Fe4S4(Cys-S)(3)(His-N)] clusters. The ligand LS3 undergoes spontaneous transfer between [Fe4S4](2+), [Fe4Se4](2+), and [MoFe3S4](3+) cores in reactions whose equilibrium constants are near the statistical value. The ligand binding affinity order PhS- > PhO- > CN- much greater than Cl- for [Fe(4)Q(4)](2+) cores was established. When taken together with earlier results from this laboratory,a comprehensive picture of ligand binding to single iron sires in [Fe(4)Q(4)](2+) dusters emerges.