Intramolecular Hydrogen Bonding Enhances Stability and Reactivity of Mononuclear Cupric Superoxide Complexes,Journal of the American Chemical Society

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Intramolecular Hydrogen Bonding Enhances Stability and Reactivity of Mononuclear Cupric Superoxide Complexes
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2018-06-29 , DOI: 10.1021/jacs.8b04671
Mayukh Bhadra ₁ , Jung Yoon C Lee ₁ , Ryan E Cowley ₂ , Sunghee Kim ₁ , Maxime A Siegler ₁ , Edward I Solomon ₂ , Kenneth D Karlin ₁

Affiliation

[(L)CuII(O2•-)]+ (i.e., 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 abstraction (HAA) of phenolic O-H bonds. Spectroscopic properties of the superoxo complexes and their azido analogues, [(L)CuII(N3-)]+, also systematically change as a function of ligand H-bonding capability.

中文翻译：

分子内氢键增强单核超氧化物铜配合物的稳定性和反应性

[(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。

更新日期：2018-06-29

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