(Fe(II)S(Me2)N4(tren))PF6 | 374607-23-5

• 英文名称: (Fe(II)S(Me2)N4(tren))PF6
• 英文别名: [Fe(S(Me2)N4(tren))][PF6]
• CAS: 374607-23-5
• 化学式: C₁₁H₂₅FeN₄S*F₆P
• 分子量: 446.223
• InChiKey: MICGZUFBDMZVEZ-YZEJZXAXSA-M

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：

  (Fe(II)S(Me2)N4(tren))PF6 、 氧气 以 not given 为溶剂， 生成
  参考文献：
  名称：

  对硫醇连接的 Fe(II) 络合物与双氧和超氧化物反应性的空间和电子控制：可逆的 mu-氧二聚体形成。

  摘要：

  检查硫醇盐连接的五配位复合物 [FeII(SMe2N4(tren))]+ (1) 和双氧之间的反应性，以确定即使在 O2 存在时是否也能促进 O2 活化（类似于金属酶细胞色素 P450 的活化）顺式（而不是反式）与硫醇盐结合。我们小组之前的工作表明，[FeII(SMe2N4(tren))]+ (1) 在质子源存在下很容易与超氧化物 (O2-) 反应，通过 Fe(III)-OOH 中间体提供 H2O2，从而提供金属酶超氧化物还原酶（SOR）的仿生模型。将 O2 添加到 1 中得到双核 mu-氧桥 [FeIII(SMe2N4(tren))]2(mu2-O)(PF6)2.3MeCN (3)。在低温下，在质子溶剂中，可以检测到中间体，其详细信息将成为另一篇论文的主题。尽管硫醇盐配体似乎不会干扰无支撑的 mu-oxo 桥的计量参数（Fe-O= 1.807(8) A，Fe-O-Fe= 155.3(5)

  DOI：

  10.1021/ic0491884
• 作为产物：
  描述：

  3-mercapto-3-methyl-butan-2-one 、 三(2-氨基乙基)胺 、 三氯化铁 以 甲醇 为溶剂， 生成 (Fe(II)S(Me2)N4(tren))PF6
  参考文献：
  名称：

  Modeling the Reactivity of Superoxide Reducing Metalloenzymes with a Nitrogen and Sulfur Coordinated Iron Complex

  摘要：

  The synthesis and structure of a five-coordinate Fe(II) complex, [(FeSN4)-S-II-N-Me2 (tren)](PF6) (1), which models the reactive properties of superoxide reductases (SORs), is reported. SORs catalyze the reduction of superoxide to peroxide in anaerobic organisms, thereby avoiding the O-2 formed in the more typical superoxide degradation enzyme superoxide dismutase (SOD). The thiolate ligand contained in model 1, as well as in SORs appears to play an important role in promoting SOR activity.

  DOI：

  10.1021/ic010221l

文献信息

• Synthetic Models for the Cysteinate-Ligated Non-Heme Iron Enzyme Superoxide Reductase:  Observation and Structural Characterization by XAS of an Fe^III−OOH Intermediate
  作者：Jason Shearer、Robert C. Scarrow、Julie A. Kovacs

  DOI：10.1021/ja012722b

  日期：2002.10.1

  reductases (SORs) belong to a new class of metalloenzymes that degrade superoxide by reducing it to hydrogen peroxide. These enzymes contain a catalytic iron site that cycles between the Fe(II) and Fe(III) states during catalysis. A key step in the reduction of superoxide has been suggested to involve HO(2) binding to Fe(II), followed by innersphere electron transfer to afford an Fe(III)-OO(H) intermediate.

  超氧化物还原酶 (SOR) 属于一类新的金属酶，可通过将超氧化物还原为过氧化氢来降解超氧化物。这些酶包含一个催化铁位点，在催化过程中在 Fe(II) 和 Fe(III) 状态之间循环。已建议还原超氧化物的关键步骤是将 HO(2) 与 Fe(II) 结合，然后进行内球电子转移以提供 Fe(III)-OO(H) 中间体。在本文中，超氧化物诱导合成亚铁 SOR 模型 ([Fe(II)(S(Me2)N(4)(tren))](+) (1)) 提供 [Fe( III)(S(Me2)N(4)(tren)(solv))](2+) (2-solv) 被报道。XANES 光谱显示 1 在甲醇溶液中保持五配位。在-90 摄氏度的 MeOH 中，1 与 KO(2) 反应，形成中间体 (3)，其特征是 LMCT 带中心位于 452(2780) nm，和低自旋状态（S = 1/2），基于其轴向 EPR 谱（g（垂直）=
• Superoxide Oxidation by a Thiolate-Ligated Iron Complex and Anion Inhibition
  作者：Maksym A. Dedushko、Jessica H. Pikul、Julie A. Kovacs

  DOI：10.1021/acs.inorgchem.1c00336

  日期：2021.5.17

  showed that the reduced thiolate-ligated [FeII(SMe2N4(tren))]+ (1) is capable of reducing O2•– via a proton-dependent inner-sphere mechanism involving a transient Fe(III)-OOH intermediate. A transient ferric-superoxo intermediate, [FeIII(SMe2N4(tren))(O2)]+ (3), is detected by electronic absorption spectroscopy at −130 °C in the reaction between 1ox-THF and KO2 and shown to evolve O2 upon slight warming

  超氧化物 (O 2 •– ) 是一种有毒自由基，通过分子氧 (O 2 )的偶然还原产生，这与许多人类疾病状态有关。非血红素铁酶，超氧化物还原酶 (SOR) 和超氧化物歧化酶 (SOD)，分别通过还原提供 H 2 O 2和歧化提供 O 2和 H 2 O 2来解毒 O 2 •–。前者在配位球中含有硫醇盐，已提出防止 O 2 •–氧化为 O 2。本文描述的工作表明，与此相反，氧化硫醇盐连接的 [FeIII (S Me2 N 4 (tren)(THF)] 2+ ( 1 ox -THF ) 能够将 O 2 •–氧化为 O 2。配位阴离子 Cl –和 OAc –显示出抑制分子氧的释放，这意味着一种内球机制。以前我们表明，还原的硫醇盐连接的 [Fe II (S Me2 N 4 (tren))] + ( 1 ) 能够还原 O 2 •–通过涉及瞬态 Fe(III)-OOH 中间体的质子依赖性内球机制。瞬态三价铁-超氧中间体
• Investigation of the Mechanism of Formation of a Thiolate-Ligated Fe(III)-OOH
  作者：Elaine Nam、Pauline E. Alokolaro、Rodney D. Swartz、Morgan C. Gleaves、Jessica Pikul、Julie A. Kovacs

  DOI：10.1021/ic101776m

  日期：2011.3.7

  Kinetic studies aimed at determining the most probable mechanism for the proton-dependent [Fe-II((SN4)-N-Me2(tren))](+) (1) promoted reduction of superoxide via a thiolate-ligated hydroperoxo intermediate [Fe-III((SN4)-N-Me2(tren))(OOH)](+) (2) are described. Rate laws are derived for three proposed mechanisms, and it is shown that they should conceivably be distinguishable by kinetics. For weak proton donors with pK(a(HA)) > pK(a(HO2)) rates are shown to correlate with proton donor pK(a), and display first-order dependence on iron, and half-order dependence on superoxide and proton donor HA. Proton donors acidic enough to convert O-2(-) to HO2 (in tetrahydrofuran, THF), that is, those with pK(a(HA)) < pK(a(HO2)), are shown to display first-order dependence on both superoxide and iron, and rates which are independent of proton donor concentration. Relative pK(a) values were determined in THF by measuring equilibrium ion pair acidity constants using established methods. Rates of hydroperoxo 2 formation displays no apparent deuterium isotope effect, and bases, such as methoxide, are shown to inhibit the formation of 2. Rate constants for p-substituted phenols are shown to correlate linearly with the Hammett substituent constants sigma(-). Activation parameters (Delta H double dagger = 2.8 kcal/mol, Delta S double dagger = -31 eu) are shown to be consistent with a low-barrier associative mechanism that does not involve extensive bond cleavage. Together, these data are shown to be most consistent with a mechanism involving the addition of HO2 to 1 with concomitant oxidation of the metal ion, and reduction of superoxide (an "oxidative addition" of sorts), in the rate-determining step. Activation parameters for MeOH- (Delta H double dagger = 13.2 kcal/mol and Delta S double dagger = -24.3 eu), and acetic acid- (Delta H double dagger = 8.3 kcal/mol and Delta S double dagger = -34 eu) promoted release of H2O2 to afford solvent-bound [Fe-III((SN4)-N-Me2(tren))(OMe)](+) (3) and [Fe-III((SN4)-N-Me2(tren))(O(H)Me)](+) (4), respectively, are shown to be more consistent with a reaction involving rate-limiting protonation of an Fe(III)-OOH, than with one involving rate-limiting O-O bond cleavage. The observed deuterium isotope effect (k(H)/k(D) = 3.1) is also consistent with this mechanism.