摄影诱导的O2-依赖的非海姆铁 (III) 复合物的逐步氧化脱糖
Christina Wegeberg1,2, Víctor M Fernández-Alvarez3, Adiran de Aguirre3
1Department of Physics, Chemistry and Pharmacy , University of Southern Denmark , Campusvej 55 , DK-5230 Odense M, Denmark.
Journal of the American Chemical Society
|October 23, 2018
概括
在紫外线照射下,铁复合物[Fe{tpena) ]2+经历O2-依赖的N-甲基碳氧化,产生新的铁复合物. 本研究详述了反应途径,确定了关键的铁中间体及其结构.
科学领域:
- 协调化学
- 摄影化学
- 生物有机化学
背景情况:
- 铁复合物在生物系统和催化过程中至关重要.
- 了解铁复合物的光化学转化对于开发新的催化过程至关重要.
研究的目的:
- 在近紫外线照射下研究铁 (III) 复合物[Fe (tpena) ]2+的O2依赖的N-甲基碳氧化.
- 描述反应中间体并阐明反应机制.
主要方法:
- 时间解析的紫外线吸收,莫斯尔,EPR和拉曼光谱.
- 密度函数理论 (DFT) 的计算.
- 结晶学研究
主要成果:
- 无可逆转的O2依赖的N-甲基化[Fe{tpena}]2+到[Fe{II}{SBPy3}{MeCN}]2+.
- 两种基于铁的中间体的光谱鉴定:一种低旋转铁 (II) 基联体复合物和一种高旋转铁 (III) 氧化物物.
- DFT计算支持一个涉及Fe ((IV) -oxo和随后的原子抽象的机制.
结论:
- 这项研究揭示了铁复合物的新型光化学反应途径.
- 已经确定了关键的中间体和N-脱甲基化的整体机制.
- 这些发现有助于了解铁介导的氧化还原过程和配体转化.
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