d9-(t)BuOOH | 173282-82-1

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 卤代烷
• 英文名称: d9-(t)BuOOH
• CAS: 173282-82-1
• 化学式: C₄H₁₀O₂
• 分子量: 99.0507
• InChiKey: CIHOLLKRGTVIJN-GQALSZNTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.27
• 重原子数：
  6.0
• 可旋转键数：
  0.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  29.46
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (N,N'-bis(2-pyridylmethyl)-N,N'-dimethyl-trans-1,2-diaminocyclohexane)bis(trifluoromethylsulfonato)iron(II) 、 d9-(t)BuOOH 以 二氯甲烷 为溶剂， 生成 (N,N'-bis(2-pyridylmethyl)-N,N'-dimethyl-trans-1,2-diaminocyclohexane)(OH)((CD3)3COO)iron(IV) triflate
  参考文献：
  名称：

  高价非血红素铁。来自普通铁 (II) 前体的两种不同的铁 (IV) 物种

  摘要：

  [Fe(II)(β-BPMCN)(OTf)2] (1, BPMCN = N,N'-双(2-吡啶基甲基)-N,N'-二甲基-反式-1,2-二氨基环己烷)的反应在低温下用 tBuOOH 生成烷基过氧铁 (III) 中间体 2 在 CH2Cl2 中和 2-NCMe 在 CH3CN 中。在 -45 摄氏度及以上时，2-NCMe 以 90% 的产率转化为淡绿色物种 3（λ(max) = 753 nm，epsilon = 280 M(-1) cm(-1))，标识为 [Fe (IV)(O)(BPMCN)(NCCH3)]2+ 与其他非血红素 [Fe(IV)(O)(L)]2+ 配合物的比较。在低于 -55 摄氏度的 CH2Cl2 中，2 会衰变形成深绿松石 4（λ(max) = 656, 845 nm；epsilon = 4000, 3600 M(-1) cm(-1)），配制为前所未有的烷基过氧化铁(IV)

  DOI：

  10.1021/ja0438765
• 作为产物：
  描述：

  d9-tert-butylmagnesium chloride 在 氧气 作用下， 以 乙醚 为溶剂， 生成 d9-(t)BuOOH
  参考文献：
  名称：

  Models for Nonheme Iron Intermediates:  Structural Basis for Tuning the Spin States of Fe(TPA) Complexes

  摘要：

  Our efforts to model the oxygen activation chemistry of nonheme iron enzymes have yielded transient intermediates with novel properties. These properties can be dramatically affected by the introduction of a 6-methyl substituent on the pendant pyridines of the tetradentate ligand TPA (TPA = tris(2-pyridylmethyl)amine). A series of Fe(TPA) complexes has thus been synthesized and characterized to provide the structural basis for these dramatic effects. The following complexes have been obtained: [Fe(L)(CH3CN)(2)](ClO4)(2) (1, L = TPA; 2, L = 6-MeTPA; 3, L = 6-Me(2)TPA; 4, L = 6-Me(3)TPA) and [Fe(L)(acac)](ClO4)(2) (5, L = TPA; 6, L = 5-Me(3)TPA; 7, L = 6-MeTPA). As indicated by H-1 NMR and/or EPR, 1, 5, and 6 wish no 6-methyl substituent are low spin, while complexes 2, 3, 4, and 7 with at least one 6-methyl substituent are all high spin, with higher redox potentials than their low-spin counterparts. The ligands with 6-methyl substituents thus favor a metal center with a larger ionic radius, i.e., Fe-II over Fe-III and high spin over low spin. Careful scrutiny of the crystal structures of 1, 4, 6, and 7 reveals that one hydrogen of the 6-methyl group is only 2.7 Angstrom away from the metal center in the high-spin complexes. Its presence thus prevents the pyridine nitrogen from forming an Fe-N bond shorter than 2.1 Angstrom as required for an iron center to adopt a low-spin configuration. This steric effect of the 6-methyl substituent serves as a simple but very useful ligand design tool to tune the electronic properties of the metastable alkylperoxoiron(III) species derived from the reactions of 1-4 with tert-butyl hydroperoxide. These intermediates serve as models for low-spin and high-spin peroxoiron(III) species in the reaction cycles of the antitumor drug bleomycin and lipoxygenase, respectively. Similar principles apply in the design of nonheme diiron(II) complexes that reversibly bind dioxygen and of high-valent bis(mu-oxo)diiron complexes that model the high-valent intermediates in the redox cycles of nonheme diiron enzymes such as methane monooxygenase and ribonucleotide reductase.

  DOI：

  10.1021/ja9638521

文献信息

• N-Terminal amino acid side-chain cleavage of chemically modified peptides in the gas phase: A mass spectrometry technique for N-terminus identification
  作者：A CHACON、D MASTERSON、H YIN、D LIEBLER、N PORTER

  DOI：10.1016/j.bmc.2006.05.060

  日期：2006.9.15

  the b or y-ion series in a peptide MS/MS spectrum as well as identification of the b1 - and yn-1 -ions can facilitate de novo analyses. Therefore, it is valuable to identify either amino-acid terminus. In previous work, we have demonstrated that peptides modified at the epsilon-amino group of lysine as a t-butyl peroxycarbamate derivative undergo free radical promoted peptide backbone fragmentation under

  尽管基因组数据库已成为蛋白质组学分析的关键，但是从头测序对于研究基因组尚未完成的生物仍然至关重要。另外，翻译后修饰对数据库搜索提出了挑战。识别肽段MS / MS光谱中的b或y离子系列以及鉴定b1和yn-1离子可以促进从头分析。因此，鉴定任一氨基酸末端是有价值的。在以前的工作中，我们已经证明，在低能量碰撞诱导解离（CID）条件下，赖氨酸的ε-氨基修饰的肽作为过氧氨基甲酸叔丁酯衍生物会经历自由基促进的肽骨架断裂。在这里，我们探讨了修饰为过氧氨基甲酸叔丁酯的N端氨基的化学性质。用芳基叔丁基过氧碳酸酯研究了N-末端胺向简单氨基酸和肽的过氧氨基甲酸酯的转化。对过氧氨基甲酸酯加合物的ESI-MS / MS分析提供了与N端侧链（R）的中性损失相对应的产物离子的证据，从而鉴定了该残基。由N末端残基侧链损失（-R）形成的产物离子的进一步碎裂（MS3）显示b离子的m / z位移等于R的中性损失，因此标记了b离
• Electronic Structure and Reactivity of High-Spin Iron−Alkyl- and −Pterinperoxo Complexes
  作者：Nicolai Lehnert、Kiyoshi Fujisawa、Edward I. Solomon

  DOI：10.1021/ic020496g

  日期：2003.1.1

  Fe(III) d orbital. For the TPA complex the pi v* CT is at 560 nm while the pi h* CT is to higher energy than 250 nm. These spectroscopic differences between four- and six-coordinate Fe(III)-OOR complexes are interpreted on the basis of their different ligand fields. In addition, the electronic structure of Fe-OOPtn complexes with the biologically relevant pterinperoxo ligand are investigated. Substitution

  四配位高自旋[FeIII（L3）（OOtBu）] +配合物的光谱性质和电子结构（1; L3 =氢三（3-叔丁基-5-异丙基-1-吡唑基）硼酸酯; tBu =研究叔丁基）并将其与六配位高自旋[Fe（6-Me3TPA）（OHx）（OOtBu）] x +系统（TPA =三（2-吡啶基甲基）胺，x = 1或2）进行比较较早[Lehnert，N .; 何润恩 小Que，L. 所罗门（EIJ Am。）化学 Soc。2001，123，12802-12816]。配合物1的特征是在889和830 cm-1处的拉曼特征被分配给OO拉伸（与对称CC拉伸混合），并在625 cm-1处具有对应于nu（Fe-O）的谱带。UV-vis光谱显示了在510 nm处从烷基过氧pi v *（v =垂直于COO平面）到Fe（III）的轨道的电荷转移（CT）跃迁。在370 nm处从MCD识别出第二个CT，该CT被指定为从pi h *（h
• Stability and reactivity of low-spin ferric hydroperoxo and alkylperoxo complexes with bipyridine and phenantroline ligands
  作者：A.P Sobolev、D.E Babushkin、E.P Talsi

  DOI：10.1016/s1381-1169(00)00197-7

  日期：2000.10

  In this work the first-order rate constants of self-decomposition of hydroperoxo and alkylperoxo complexes [Fe(bpr)(2)(OOH)Py](NO3)(2) (2a-Py), [Fe(phen)(2)(OOH)Py](NO3)(2) (2b-Py) and [Fe(bpy)(2)(OOtBu)CH3CN](NO3)(2) (3a-CH3CN) were determined in the presence of various substrates and at various temperatures. It was observed, that the alkylperoxo species are far less stable than corresponding hydroperoxo intermediates, k = 1.2 x 10(-2) s(-1) (3a-CH3CN in CH,CN at - 10 degrees C) and k = 2 x 10(-4) s(-1) (2a-Py in CH3CN at - 10 degrees C). The sixth ligand (Py in 2a-Py and 2b-Py; CH,CN in 3a-CH3CN) can be replaced by other donor molecules B in appropriate solvent systems. Using d(9)-tBuOOH, D-2 NMR signals of tBuOO moieties of complexes 3a-CH3CN, 3a-CH3OH and 3a-H2O were observed. The rate of decomposition of hydroperoxo complexes [Fe(bpy)(2)(OOH)B](NO3)(2) (2a-B), where B are derivatives of Py (3-Br-Py, 3-Me-Py, 4-Me-Py and 4-Me2N-Py) increases with the growth of basisity of B (push effect). Such effect is markedly smaller for alkylperoxo species [Fe(bpy)(2)(OOtBu)B](NO3)(2) (3a-B). The addition of organic substrates (cyclohexane, cyclohexene, methyl phenyl sulfide) in concentrations up to 3 M at -10 degrees C to +20 degrees C does not noticeably change the rate of self-decomposition of 2a-B, [Fe(phen)(2)(OOH)B](NO3)(2) (2b-B) and 3a-B. Thus the intermediates concerned do not directly react with organic substrates. The reactivity patterns of 2a-B, 2b-B and 3a-B were characteristic for free radical oxidation. OH. and HO2. radicals were trapped in solution containing 2a-Py, and tBuOO(.) free radicals were detected in solution in the presence of 3a-B. The determined rates of self-decomposition of complexes 2a-B, 2b-B and 3a-B can be used for evaluation of the upper limit for their reactivity towards organic substrates. (C) 2000 Elsevier Science B.V. All rights reserved.