[(BA)Cu^I]B(C₆F₅)₄ | 1413355-84-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [(BA)Cu^I]B(C₆F₅)₄
• 英文别名: [(BA)Cu^I]B(C6F5)4；[(BA)Cu^I]BArF
• CAS: 1413355-84-6
• 化学式: C₂₄BF₂₀*C₂₅H₂₅CuN₅
• 分子量: 1138.1
• InChiKey: WIBABLRNISZMKY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [(BA)Cu^I]B(C₆F₅)₄ 、 双氧水 以 丙酮 为溶剂， 以100%的产率得到[(BA)Cu^II(hydroperoxo)]⁺
  参考文献：
  名称：

  Coordination Chemistry and Reactivity of a Cupric Hydroperoxide Species Featuring a Proximal H-Bonding Substituent

  摘要：

  At -90 degrees C in acetone, a stable hydroperoxo complex [(BA)(CuOOH)-O-II](+) (2) (BA, a tetradentate N-4 ligand possessing a pendant -N(H)CH2C6H5 group) is generated by reacting [(BA)Cu-II(CH3COCH3)](2+) with only 1 equiv of H2O2/Et3N. The exceptional stability of 2 is ascribed to internal H-bonding. Species 2 is also generated in a manner not previously known in copper chemistry, by adding 1.5 equiv of H2O2 (no base) to the cuprous complex [(BA)Cu-I](+). The broad implications for this finding are discussed. Species 2 slowly converts to a mu-1,2-peroxodicopper(II) analogue (3) characterized by UV-vis and resonance Raman spectroscopies. Unlike a close analogue not possessing internal H-bonding, 2 affords no oxidative reactivity with internal or external substrates. However, 2 can be protonated to release H2O2, but only with HClO4, while 1 equiv Et3N restores 2.

  DOI：

  10.1021/ic302071e

文献信息

• Intramolecular Hydrogen Bonding Enhances Stability and Reactivity of Mononuclear Cupric Superoxide Complexes
  作者：Mayukh Bhadra、Jung Yoon C. Lee、Ryan E. Cowley、Sunghee Kim、Maxime A. Siegler、Edward I. Solomon、Kenneth D. Karlin

  DOI：10.1021/jacs.8b04671

  日期：2018.7.25

  , cupric-superoxo) complexes, as the first and/or key reactive intermediates in (bio)chemical Cu-oxidative processes, including in the monooxygenases PHM and DβM, have been systematically stabilized by intramolecular hydrogen bonding within a TMPA ligand-based framework. Also, gradual strengthening of ligand-derived H-bonding dramatically enhances the [(L)CuII(O2•-)]+ reactivity toward hydrogen-atom

  [(L)CuII(O2•-)]+（即铜-超氧）配合物，作为（生物）化学铜氧化过程（包括单加氧酶 PHM 和 DβM）中的第一个和/或关键反应中间体，已被通过基于 TMPA 配体的框架内的分子内氢键系统地稳定。此外，配体衍生的氢键的逐渐增强显着增强了 [(L)CuII(O2•-)]+ 对酚 OH 键的氢原子夺取 (HAA) 的反应性。超氧配合物及其叠氮类似物 [(L)CuII(N3-)]+ 的光谱特性也会随着配体氢键能力的变化而系统地变化。
• Peroxynitrite chemistry derived from nitric oxide reaction with a Cu(<scp>ii</scp>)–OOH species and a copper mediated NO reductive coupling reaction
  作者：Sunghee Kim、Maxime A. Siegler、Kenneth D. Karlin

  DOI：10.1039/c3cc47942k

  日期：——

  New peroxynitrite-copper chemistry ensues via addition of nitric oxide ( NO(g)) to a Cu(II)-hydroperoxo species. In characterizing the system, the ligand-Cu(i) complex was shown to effect a seldom observed NO(g) reductive coupling reaction. Biological implications are discussed.

  通过将一氧化氮 (NO(g)) 添加到 Cu(II)-氢过氧物质中，产生新的过亚硝酸盐-铜化学反应。在表征该系统时，配体-Cu(i) 络合物显示出很少观察到的 NO(g) 还原偶联反应。讨论了生物学意义。