trans-Fe(II)(N-MeIm)2(Cl)2(MeOH)2 | 129285-54-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: trans-Fe(II)(N-MeIm)2(Cl)2(MeOH)2
• 英文别名: trans-Fe(II)(N-methylimidazole)2(Cl2)(MeOH)2；Dichloroiron;methanol;1-methylimidazole
• CAS: 129285-54-7
• 化学式: C₁₀H₂₀Cl₂FeN₄O₂
• 分子量: 355.047
• InChiKey: YRMHMYRVHAHPDD-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  1.43
• 重原子数：
  19
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  76.1
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  trans-Fe(II)(N-MeIm)2(Cl)2(MeOH)2 、 在 air 作用下， 以 甲醇 为溶剂， 生成 Fe(III)2(μ-OMe)2(1,3-bis(2-hydroxybenzamodo)butane)2
  参考文献：
  名称：

  Synthesis and characterization of a family of binuclear non-heme iron monooxygenase model compounds: Evidence for a “phenolate/amide carbonyl (PAC) shift” upon oxidation

  摘要：

  A series of binuclear iron compounds has been synthesized using diamide, bis-phenolate ligands in which the carbon-linker between the amide nitrogen atoms has been varied. Two diferrous compounds in the series, Fe-2(II)(H(2)Hbach)(2)(N-MeIM)(2) and Fe-2(II)(H(2)Hbame)(2)(N-MeIM)(2) along with their two-electron oxidized, di-mu-methoxy-bridged counterparts, Fe-III(H(2)Hbach)(2)(OMe)(2) and Fe-III(H(2)Hbame)(2)(OMe)(2) have been crystallographically characterized, as have the di-mu-methoxy compounds Fe-2(III)(H(2)Hbap)(2)(OMe)(2); Fe-2(III)(H(2)Hbabn)(2)(OMe)(2) and Fe-2(III)(H(2)Hbapen)(2)(OMe)(2) (H(2)Hbab = 1,2-bis(2-hydroxybenzamido) benzene, H(2)Hbach = trans-1,2-bis(2-hydroxybenzamido) cyclohexane, H(2)Hbame = 1,2-bis(2-hydroxybenzamido) ethane, H(2)Hbap = 1,3-bis(2-hydroxybenzamido) propane, H(2)Hbabn = 1,4-bis(2-hydroxybenzamido) butane, H(2)Hbapen = 1,5-bis(2-hydroxybenzamido) pentane, N-MeIM = N-methylimidazole and OMe = methoxide). Fe-2(II)(H(2)Hbach)(2)(N-MeIM)(2) and Fe-2(II)(H(2)Hbame)(2)(N-MeIM)(2) are structurally very similar to previously reported diferrous compounds of this family of ligands that have been shown to be active as oxygen atom transfer catalysts. Flexibility in the carbon-linker allows some variability in the orientation of the phenolate arms of the ligands in the diferric di-mu-methoxy compounds, but the Fe2O2 core remains largely unchanged across the series. Two-electron oxidation of the ferrous compounds in methanol shows a substantial ligand rearrangement that is consistent with other spectroscopic, electrochemical and kinetic investigations. The loss of both phenolate bridges upon oxidation is reminiscent of the "carboxylate shift" observed in binuclear non-heme enzymes and could provide insight into the driving force behind this family of compounds' function as a catalyst. (c) 2008 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.ica.2008.09.036
• 作为产物：
  描述：

  N-甲基咪唑 、 iron(II) chloride 在 CH₃OH 作用下， 以 甲醇 为溶剂， 以74.5%的产率得到trans-Fe(II)(N-MeIm)2(Cl)2(MeOH)2
  参考文献：
  名称：

  Synthesis, structure, and electronic characterization of reactive diiron(II) 1,2-bis(2-hydroxybenzamido)benzene complexes as models for methane monooxygenase

  摘要：

  The dinuclear iron(II) compound [Fe2(H2Hbab)2(N-MeIm)2], 10, and its DMF solvated form, [Fe2(H2Hbab)2-(DMF)2(N-MeIm)], 11 (H4Hbab = 1,2-bis(2-hydroxybenzamido)benzene), were synthesized, and their structures were determined by X-ray crystallography. Compound 10 crystallizes in triclinic space group PT with a = 9.969 (4) angstrom, b = 12.754 (5) angstrom, c = 9.919 (7) angstrom, alpha = 100.60 (5)degrees, beta = 18.40 (4)degrees, gamma = 77.42 (3)degrees, and Z = 2. The compound is centrosymmetric with two equivalent FeNO4 trigonal-bipyramidal coordination spheres composed of amide oxygen atoms, terminal and bridging phenolate oxygen atoms, and a single nitrogen from N-MeIm. Compound 11 crystallizes in triclinic space group P(I) with a = 13.198 (4) angstrom, b = 20.294 (6) angstrom, c = 9.651 (5) angstrom, a = 90.29 (3)degrees, beta = 98.70 (3)degrees, gamma = 101.54 (2)degrees, and Z = 2. The dinuclear compound 11 contains one FeNO4 and one FeO6 coordination sphere in which one N-MeIm has been displaced by two solvent DMF molecules. The asymmetric Fe2O2 rhombs contain d(Fe-Fe) of 3.165 (7) angstrom (10) and 3.190 (4) angstrom (11), with Fe-O-Fe angles of 98.9 (3)degrees (10) and 97.7 (5)degrees and 100.7 (5)degrees (11). Spectroscopic properties of 10 and 11 are compared to those of fully reduced methane monooxygenase (MMO) and the B2 subunit of ribonucleotide reductase (RRB2). The optical spectrum (270-280 nm, 312 nm, epsilon-M = 30000 vs 280-290 nm for MMO), magnetic exchange properties (spin exchange coupling constant J almost-equal-to +2.5 cm-1 vs weak ferromagnetic coupling for MMO), and Mossbauer spectroscopic parameters (delta = 1.1 8 mm s-1, DELTA-E(Q) = 3.26 mm s-1 for 10 and delta-1 = 1.24 mm s-1, DELTA-E(Q1), = 3.08 MM S-1, delta-2 = 1.29 mm s-1 and DELTA-E(Q2) = 2.54 mm s-1 for frozen DMF solutions of 10 vs delta = 1.30 mm s-1 and DELTA-E(Q) = 3.14 mm s-1 for MMO and delta = 1.26 mm s-1 and DELTA-E(Q) = 3.13 mm s-1 for RRB2) are presented. Cyclic and square-wave voltammetric studies of 11 in DMF revEaled two quasi-reversible one-electron oxidation steps at -500 and -250 mV versus SCE corresponding to [Fe2+,Fe2+] --> [Fe2+,Fe3+] and [Fe2+,Fe3+] --> [Fe3+,Fe3+] core oxidation state transformations. Thus, the mixed-valence species is thermodynamically stable with a comproportionation constant K(com) = 1.7 X 10(4). A comparison of these results with those reported for MMO (-135 and +48 mV vs NHE) is presented. The proton NMR spectrum of DMSO solutions of 11 is reported as are electron spin resonance studies which reveal integer spin features at g almost-equal-to 12 (vs g almost-equal-to 16 for MMO and RRB2) in frozen DMF glasses at 4.2 K.

  DOI：

  10.1021/ja00023a016

文献信息

• Stassinopoulos, Adonis; Caradonna, John P., Journal of the American Chemical Society, 1990, vol. 112, # 19, p. 7071 - 7073
  作者：Stassinopoulos, Adonis、Caradonna, John P.

  DOI：——

  日期：——
• Synthesis and characterization of a family of binuclear non-heme iron monooxygenase model compounds: Evidence for a “phenolate/amide carbonyl (PAC) shift” upon oxidation
  作者：Patrick J. Cappillino、Paul C. Tarves、Gerard T. Rowe、Andrew J. Lewis、Mark Harvey、Corina Rogge、Adonis Stassinopoulos、Wayne Lo、William H. Armstrong、John P. Caradonna

  DOI：10.1016/j.ica.2008.09.036

  日期：2009.5

  A series of binuclear iron compounds has been synthesized using diamide, bis-phenolate ligands in which the carbon-linker between the amide nitrogen atoms has been varied. Two diferrous compounds in the series, Fe-2(II)(H(2)Hbach)(2)(N-MeIM)(2) and Fe-2(II)(H(2)Hbame)(2)(N-MeIM)(2) along with their two-electron oxidized, di-mu-methoxy-bridged counterparts, Fe-III(H(2)Hbach)(2)(OMe)(2) and Fe-III(H(2)Hbame)(2)(OMe)(2) have been crystallographically characterized, as have the di-mu-methoxy compounds Fe-2(III)(H(2)Hbap)(2)(OMe)(2); Fe-2(III)(H(2)Hbabn)(2)(OMe)(2) and Fe-2(III)(H(2)Hbapen)(2)(OMe)(2) (H(2)Hbab = 1,2-bis(2-hydroxybenzamido) benzene, H(2)Hbach = trans-1,2-bis(2-hydroxybenzamido) cyclohexane, H(2)Hbame = 1,2-bis(2-hydroxybenzamido) ethane, H(2)Hbap = 1,3-bis(2-hydroxybenzamido) propane, H(2)Hbabn = 1,4-bis(2-hydroxybenzamido) butane, H(2)Hbapen = 1,5-bis(2-hydroxybenzamido) pentane, N-MeIM = N-methylimidazole and OMe = methoxide). Fe-2(II)(H(2)Hbach)(2)(N-MeIM)(2) and Fe-2(II)(H(2)Hbame)(2)(N-MeIM)(2) are structurally very similar to previously reported diferrous compounds of this family of ligands that have been shown to be active as oxygen atom transfer catalysts. Flexibility in the carbon-linker allows some variability in the orientation of the phenolate arms of the ligands in the diferric di-mu-methoxy compounds, but the Fe2O2 core remains largely unchanged across the series. Two-electron oxidation of the ferrous compounds in methanol shows a substantial ligand rearrangement that is consistent with other spectroscopic, electrochemical and kinetic investigations. The loss of both phenolate bridges upon oxidation is reminiscent of the "carboxylate shift" observed in binuclear non-heme enzymes and could provide insight into the driving force behind this family of compounds' function as a catalyst. (c) 2008 Elsevier B. V. All rights reserved.
• Synthesis, structure, and electronic characterization of reactive diiron(II) 1,2-bis(2-hydroxybenzamido)benzene complexes as models for methane monooxygenase
  作者：A. Stassinopoulos、G. Schulte、G. C. Papaefthymiou、J. P. Caradonna

  DOI：10.1021/ja00023a016

  日期：1991.11

  The dinuclear iron(II) compound [Fe2(H2Hbab)2(N-MeIm)2], 10, and its DMF solvated form, [Fe2(H2Hbab)2-(DMF)2(N-MeIm)], 11 (H4Hbab = 1,2-bis(2-hydroxybenzamido)benzene), were synthesized, and their structures were determined by X-ray crystallography. Compound 10 crystallizes in triclinic space group PT with a = 9.969 (4) angstrom, b = 12.754 (5) angstrom, c = 9.919 (7) angstrom, alpha = 100.60 (5)degrees, beta = 18.40 (4)degrees, gamma = 77.42 (3)degrees, and Z = 2. The compound is centrosymmetric with two equivalent FeNO4 trigonal-bipyramidal coordination spheres composed of amide oxygen atoms, terminal and bridging phenolate oxygen atoms, and a single nitrogen from N-MeIm. Compound 11 crystallizes in triclinic space group P(I) with a = 13.198 (4) angstrom, b = 20.294 (6) angstrom, c = 9.651 (5) angstrom, a = 90.29 (3)degrees, beta = 98.70 (3)degrees, gamma = 101.54 (2)degrees, and Z = 2. The dinuclear compound 11 contains one FeNO4 and one FeO6 coordination sphere in which one N-MeIm has been displaced by two solvent DMF molecules. The asymmetric Fe2O2 rhombs contain d(Fe-Fe) of 3.165 (7) angstrom (10) and 3.190 (4) angstrom (11), with Fe-O-Fe angles of 98.9 (3)degrees (10) and 97.7 (5)degrees and 100.7 (5)degrees (11). Spectroscopic properties of 10 and 11 are compared to those of fully reduced methane monooxygenase (MMO) and the B2 subunit of ribonucleotide reductase (RRB2). The optical spectrum (270-280 nm, 312 nm, epsilon-M = 30000 vs 280-290 nm for MMO), magnetic exchange properties (spin exchange coupling constant J almost-equal-to +2.5 cm-1 vs weak ferromagnetic coupling for MMO), and Mossbauer spectroscopic parameters (delta = 1.1 8 mm s-1, DELTA-E(Q) = 3.26 mm s-1 for 10 and delta-1 = 1.24 mm s-1, DELTA-E(Q1), = 3.08 MM S-1, delta-2 = 1.29 mm s-1 and DELTA-E(Q2) = 2.54 mm s-1 for frozen DMF solutions of 10 vs delta = 1.30 mm s-1 and DELTA-E(Q) = 3.14 mm s-1 for MMO and delta = 1.26 mm s-1 and DELTA-E(Q) = 3.13 mm s-1 for RRB2) are presented. Cyclic and square-wave voltammetric studies of 11 in DMF revEaled two quasi-reversible one-electron oxidation steps at -500 and -250 mV versus SCE corresponding to [Fe2+,Fe2+] --> [Fe2+,Fe3+] and [Fe2+,Fe3+] --> [Fe3+,Fe3+] core oxidation state transformations. Thus, the mixed-valence species is thermodynamically stable with a comproportionation constant K(com) = 1.7 X 10(4). A comparison of these results with those reported for MMO (-135 and +48 mV vs NHE) is presented. The proton NMR spectrum of DMSO solutions of 11 is reported as are electron spin resonance studies which reveal integer spin features at g almost-equal-to 12 (vs g almost-equal-to 16 for MMO and RRB2) in frozen DMF glasses at 4.2 K.