[Fe^III(octakis(4-tert-butylphenyl)-corrolazinato)] | 944329-48-0

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: [Fe^III(octakis(4-tert-butylphenyl)-corrolazinato)]
• 英文别名: [Fe^III(TBP₈Cz)]；(TBP8Cz)Fe(III)；(octakis(4-tert-butylphenyl)corrolazinato)iron(III)；(iron)(β-octakis-4-tert-butylphenylcorrolazinato)；Fe(octakis(4-tert-butylphenyl)corrolazinate)；(TBP8Cz)Fe；Fe(TBP8Cz)；Iron(3+);3,4,8,9,13,14,18,19-octakis(4-tert-butylphenyl)-6,11,16,21-tetraza-20,22,23-triazanidapentacyclo[15.2.1.12,5.17,10.112,15]tricosa-1,3,5,7,9,11,13,15(21),16,18-decaene
• CAS: 944329-48-0
• 化学式: C₉₆H₁₀₄FeN₇
• 分子量: 1411.78
• InChiKey: SMGCETUHYNPGKB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  24.98
• 重原子数：
  104
• 可旋转键数：
  16
• 环数：
  13.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  54.6
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  [Fe^III(octakis(4-tert-butylphenyl)-corrolazinato)] 在 1,2,3,4,5-pentafluoro-6-iodosylbenzene 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  McGown, Amanda J.; Kerber, William D.; Fujii, Hiroshi, Journal of the American Chemical Society, 2009, vol. 131, p. 8040 - 8048

  摘要：

  DOI：
• 作为产物：
  描述：

  (octakis(4-tert-butylphenyl)corrolazinato)oxoiron(IV) 在 [Fe(C₅H₅)2] 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 生成 [Fe^III(octakis(4-tert-butylphenyl)-corrolazinato)]
  参考文献：
  名称：

  A High-Valent Iron–Oxo Corrolazine Activates C–H Bonds via Hydrogen-Atom Transfer

  摘要：

  Oxidation of the Fe-III complex (TBP(8)Cz)Fe-III [TBP(8)Cz = octakis(4-tert-butylphenyl)corrolazinate] with O-atom transfer oxidants under a variety of conditions gives the reactive high-valent Fe(O) complex (TBP(8)Cz(+center dot))Fe-IV(O) (2). The solution state structure of 2 was characterized by XAS [d(Fe-O) = 1.64 angstrom]. This complex is competent to oxidize a range of C-H substrates. Product analyses and kinetic data show that these reactions occur via rate-determining hydrogen-atom transfer (HAT), with a linear correlation for log k versus BDE(C-H), and the following activation parameters for xanthene (Xn) substrate: Delta H-double dagger = 12.7 +/- 0.8 kcal mol(-1), Delta S-double dagger = -9 +/- 3 cal K-1 mol(-1), and KIE = 5.7. Rebound hydroxylation versus radical dimerization for Xn is favored by lowering the reaction temperature. These findings provide insights into the factors that control the intrinsic reactivity of Compound I heme analogues.

  DOI：

  10.1021/ja3018658
• 作为试剂：
  描述：

  氧杂蒽 在 [Fe^III(octakis(4-tert-butylphenyl)-corrolazinato)] 、 间氯过氧苯甲酸 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 以75%的产率得到占吨醇
  参考文献：
  名称：

  A High-Valent Iron–Oxo Corrolazine Activates C–H Bonds via Hydrogen-Atom Transfer

  摘要：

  Oxidation of the Fe-III complex (TBP(8)Cz)Fe-III [TBP(8)Cz = octakis(4-tert-butylphenyl)corrolazinate] with O-atom transfer oxidants under a variety of conditions gives the reactive high-valent Fe(O) complex (TBP(8)Cz(+center dot))Fe-IV(O) (2). The solution state structure of 2 was characterized by XAS [d(Fe-O) = 1.64 angstrom]. This complex is competent to oxidize a range of C-H substrates. Product analyses and kinetic data show that these reactions occur via rate-determining hydrogen-atom transfer (HAT), with a linear correlation for log k versus BDE(C-H), and the following activation parameters for xanthene (Xn) substrate: Delta H-double dagger = 12.7 +/- 0.8 kcal mol(-1), Delta S-double dagger = -9 +/- 3 cal K-1 mol(-1), and KIE = 5.7. Rebound hydroxylation versus radical dimerization for Xn is favored by lowering the reaction temperature. These findings provide insights into the factors that control the intrinsic reactivity of Compound I heme analogues.

  DOI：

  10.1021/ja3018658

文献信息

• Generation of a High-Valent Iron Imido Corrolazine Complex and NR Group Transfer Reactivity
  作者：Pannee Leeladee、Guy N. L. Jameson、Maxime A. Siegler、Devesh Kumar、Sam P. de Visser、David P. Goldberg

  DOI：10.1021/ic400280x

  日期：2013.4.15

  accounts for all of the observed products. The latter FeIII complex was then rationally synthesized and structurally characterized from FeIII(TBP8Cz) and OPPh3, providing an important benchmark compound for spectroscopic studies. A combination of Mössbauer and EPR spectroscopies led to the characterization of both intermediate spin (S = 3/2) and low spin (S = 1/2) FeIII corrolazines, as well as a formally

  报道了用科拉尔嗪大环化合物制备的新的高价铁末端亚氨基复合物的产生。[Fe的反应III（TBP 8 CZ）]（TBP 8锆石= octakis（4 -叔丁基苯基）corrolazinato）与可商购的氯胺-T（钠+ TsNCl - ）导致氧化N-甲苯磺酰基转移，得到[室温下在二氯甲烷/乙腈中的Fe IV（TBP 8 CZ +•）（NTs）]。该复合物的特征在于紫外可见，莫斯鲍尔（Mössbauer）（δ= −0.05 mm s –1，ΔE Q = 2.94 mm s –1）和EPR（X波段（15 K），g= 2.10，2.00）光谱，并与反应模式和DFT计算一起已被确立为铁（IV）物种反铁磁性耦合用锆石-π-阳离子自由基（š总= 1 / 2态）。与三苯基膦作为底物表明的[Fe反应性研究IV（TBP 8锆石+•）（NTS）]是一种高效的NT转移剂，得到的产物phospharane博士3个两者的
• Formation and characterization of five- and six-coordinate iron(III) corrolazine complexes
  作者：Satoshi Kurahashi、Takahisa Ikeue、Tamotsu Sugimori、Masashi Takahashi、Masahiro Mikuriya、Makoto Handa、Akira Ikezaki、Mikio Nakamura

  DOI：10.1142/s1088424612500460

  日期：2012.5

  Electronic structures of five- and six-coordinate iron(III) corrolazine complexes are determined by means of1H NMR,13C NMR, EPR, and Mössbauer spectroscopy as well as SQUID magnetometry. A series of five-coordinate complexes, [FeIII(TBP8Cz)(L)]* where the axial ligands(L) are cyanide(CN-), imidazole(HIm), 1-methylimidazole(1-MeIm), 4-(N,N-dimethylamino)pyridine(DMAP), pyridine(Py), 4-cyanopyridine(4-CNPy)

  五配位和六配位铁（III）corroazine配合物的电子结构通过以下方法确定1核磁共振氢谱，13C NMR、EPR 和 Mössbauer 光谱以及 SQUID 磁力计。一系列五坐标配合物，[Fe三（待定8Cz)(L)]* 其中轴向配体 (L) 是氰化物 (CN-)、咪唑(HIm)、1-甲基咪唑(1-MeIm)、4-(N,N-二甲氨基)吡啶(DMAP)、吡啶(Py)、4-氰基吡啶(4-CNPy)和叔丁基异氰化物(吨BuNC)，通过添加 1 到 2 equiv 获得。Fe的二氯甲烷溶液的配体三（待定8Cz）在 298 K：待定8Cz 是 2,3,7,8,12,13,17,18-八（4-叔丁基苯基）可咯嗪的三阴离子。这些配合物通常在 298 K 时显示 S = 3/2。相比之下，六配位配合物的形成取决于轴向配体的性质。同时增加 3 equiv。CN的-已完全转化 Fe三（待定8Cz) 至 (
• H2O2 Oxidations Catalyzed by an Iron(III) Corrolazine: Avoiding High-Valent Iron–Oxido Species?
  作者：William D. Kerber、Bobby Ramdhanie、David P. Goldberg

  DOI：10.1002/anie.200605156

  日期：2007.5.11