[(N,N'-bis-(2'-methyl-2'-mercaptopropyl)-1-thia-4,7-diazacyclononane(-2H))Fe]2(μ-O) | 577959-15-0

• 英文名称: [(N,N'-bis-(2'-methyl-2'-mercaptopropyl)-1-thia-4,7-diazacyclononane(-2H))Fe]2(μ-O)
• 英文别名: [(bmmp-TASN)Fe]2O
• CAS: 577959-15-0
• 化学式: C₂₈H₅₆Fe₂N₄OS₆
• 分子量: 768.869
• InChiKey: JLFMUEFWMVJSOT-UHFFFAOYSA-J

反应信息

• 作为反应物：
  描述：

  三氟甲磺酸 、 [(N,N'-bis-(2'-methyl-2'-mercaptopropyl)-1-thia-4,7-diazacyclononane(-2H))Fe]2(μ-O) 以 乙腈 为溶剂， 以75%的产率得到[((N,N'-bis-(2'-methyl-2'-mercaptopropyl)-1-thia-4,7-diazacyclononane(-2H))Fe)2OH](triflate)
  参考文献：
  名称：

  Substrate Binding Preferences and pK_aDeterminations of a Nitrile Hydratase Model Complex: Variable Solvent Coordination to [(bmmp-TASN)Fe]OTf

  摘要：

  The five-coordinate iron-dithiolate complex (N,N'-4,7-bis-(2'-methyl-2'-mercatopropyl)-1-thia-4,7-diazacyclononane)iron(III), [LFe](+), has been isolated as the triflate salt from reaction of the previously reported LFeCl with thallium triflate. Spectroscopic characterization confirms an S = 1/2 ground state in non-coordinating solvents with room temperature mu(eff) = 1.78 mu(B) and electron paramagnetic resonance (EPR) derived g-values of g(1) = 2.04, g(2) = 2.02 and g(3) = 2.01. [LFe](+) binds a variety of coordinating solvents resulting in six-coordinate complexes [LFe-solvent](+). In acetonitrile the low-spin [LFe-NCMe](+) (g(1) = 2.27, g(2) = 2.18, and g(3) = 1.98) is in equilibrium with [LFe](+) with a binding constant of K-eq = 4.7 at room temperature. Binding of H2O, DMF, methanol, DMSO, and pyridine to [LFe]+ yields high-spin six-coordinate complexes with EPR spectra that display significant strain in the rhombic zero-field splitting term E/D. Addition of 1 equiv of triflic acid to the previously reported diiron species (LFe)(2)O results in the formation of [(LFe)(2)OH]OTf, which has been characterized by X-ray crystallography. The aqueous chemistry of [LFe](+) reveals three distinct species as a function of pH: [LFe-OH2](+), [(LFe)(2)OH]OTf, and (LFe)(2)O. The pK(a) values for [LFe-OH2](+) and [(LFe)(2)OH]OTf are 5.4 +/- 0.1 and 6.52 +/- 0.05, respectively.

  DOI：

  10.1021/ic802180d
• 作为产物：
  描述：

  [(N,N'-bis-(2'-methyl-2'-mercaptopropyl)-1-thia-4,7-diazacyclononane(-2H))Fe(water)](1+) 在 NaOH 作用下， 以 水 为溶剂， 生成 [(N,N'-bis-(2'-methyl-2'-mercaptopropyl)-1-thia-4,7-diazacyclononane(-2H))Fe]2(μ-O)
  参考文献：
  名称：

  Substrate Binding Preferences and pK_aDeterminations of a Nitrile Hydratase Model Complex: Variable Solvent Coordination to [(bmmp-TASN)Fe]OTf

  摘要：

  The five-coordinate iron-dithiolate complex (N,N'-4,7-bis-(2'-methyl-2'-mercatopropyl)-1-thia-4,7-diazacyclononane)iron(III), [LFe](+), has been isolated as the triflate salt from reaction of the previously reported LFeCl with thallium triflate. Spectroscopic characterization confirms an S = 1/2 ground state in non-coordinating solvents with room temperature mu(eff) = 1.78 mu(B) and electron paramagnetic resonance (EPR) derived g-values of g(1) = 2.04, g(2) = 2.02 and g(3) = 2.01. [LFe](+) binds a variety of coordinating solvents resulting in six-coordinate complexes [LFe-solvent](+). In acetonitrile the low-spin [LFe-NCMe](+) (g(1) = 2.27, g(2) = 2.18, and g(3) = 1.98) is in equilibrium with [LFe](+) with a binding constant of K-eq = 4.7 at room temperature. Binding of H2O, DMF, methanol, DMSO, and pyridine to [LFe]+ yields high-spin six-coordinate complexes with EPR spectra that display significant strain in the rhombic zero-field splitting term E/D. Addition of 1 equiv of triflic acid to the previously reported diiron species (LFe)(2)O results in the formation of [(LFe)(2)OH]OTf, which has been characterized by X-ray crystallography. The aqueous chemistry of [LFe](+) reveals three distinct species as a function of pH: [LFe-OH2](+), [(LFe)(2)OH]OTf, and (LFe)(2)O. The pK(a) values for [LFe-OH2](+) and [(LFe)(2)OH]OTf are 5.4 +/- 0.1 and 6.52 +/- 0.05, respectively.

  DOI：

  10.1021/ic802180d

文献信息

• Synthesis and Characterization of N₂S₃X−Fe Models of Iron-Containing Nitrile Hydratase
  作者：Craig A. Grapperhaus、Ming Li、Apurba K. Patra、Selma Poturovic、Pawel M. Kozlowski、Marek Z. Zgierski、Mark S. Mashuta

  DOI：10.1021/ic026239t

  日期：2003.7.1

  recrystallized from CH(2)Cl(2)/hexane solution in the triclinic space group P1, with a = 10.5486(15) A, b = 13.0612(19) A, c = 8.1852(12) A, alpha = 96.923(2) degrees, beta = 112.729(2) degrees, gamma = 81.048(2) degrees, and Z = 1. Density functional theory (DFT) calculations of the previously communicated iron-nitrosyl complex [(bmmp-TASN)Fe(III)(NO)][BPh(4)] (4) (Inorg. Chem. 2002, 41, 1039-1041) reveal that

  基于五齿配体4,7-双（2'-甲基-2'-巯基丙基）-1-硫杂-4,7-二氮杂环壬烷）的一系列铁配合物，（bmmp-TASN）（2）（-），已合成并表征为含铁腈水合酶（NHase）的模型。氯衍生物[（bmmp-TASN）Fe（III）Cl] .0.5EtOH（1）含有不稳定的氯化物，可通过取代反应促进相关配合物的合成。复合物1是高转速的，g = 4.28。在CH（2）Cl（2）中加1的NEt（4）CN导致氰化物连接的络合物[（bmmp-TASN）Fe（III）CN] x 0.5EtOH（2），显示单个强nu（ CN）在IR区域的2083 cm（-）（1）波段。复数2是低自旋的，g（1）= 2.31，g（2）= 2.16，g（3）= 1.96。在碱性条件下，配合物1提供了一种由mu-oxo桥联的二聚Fe（III）配合物[（bmmp-TASN）Fe（III）]（2）O（3），在799 cm（-