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首页> 外文期刊>Proceedings of the National Academy of Sciences of the United States of America >O_2 reduction by a functional hemeonheme bis-iron NOR model complex
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O_2 reduction by a functional hemeonheme bis-iron NOR model complex

机译:通过功能性血红素/非血红素双铁NOR模型复合物还原O_2

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摘要

O_2 reactivity of a functional NOR model is investigated by using electrochemistry and spectroscopy. The electrochemical measurements using interdigitated electrodes show very high selectivity for 4e O_2 reduction with minimal production of partially reduced oxygen species (PROS) under both fast and slow electron flux. Intermediates trapped at cryogenic temperatures and characterized by using resonance Raman spectroscopy under single-turnover conditions indicate that an initial bridging peroxide intermediate undergoes homolytic O-O bond cleavage generating a trans hemeonheme bis-ferryl intermediate. This bis ferryl species can oxygenate 2 equivalents of a reactive substrate.
机译:通过电化学和光谱研究功能性NOR模型的O_2反应性。使用叉指式电极的电化学测量结果显示,在快速和缓慢的电子通量下,4e O_2还原的选择性非常高,而部分还原的氧物种(PROS)的生成量却最小。在低温下捕获的中间体,其特征是在单周转条件下使用共振拉曼光谱进行表征,表明初始的过氧化物过氧化物中间体经历了均相O-O键裂解,从而生成了全血红素/非血红素双轮渡中间体。该双亚丙基物质可氧化2当量的反应性底物。

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