增强的非黑米铁氧复合结合质子的氧反应性
Shan-Shan Xue1, Xiao-Xi Li1, Yong-Min Lee1
1Department of Chemistry and Nano Science, Ewha Womans University, Seoul 03760, Korea.
Journal of the American Chemical Society
|August 14, 2020
概括
在氧原子转移和电子转移反应中,质子化极大地提高了铁氧复合物的反应性. 这项研究详细介绍了质子化铁{V) -oxo四胺宏环联体复合物的合成和反应性.
科学领域:
- 协调化学
- 生物有机化学
- 氧化催化
背景情况:
- 酸对金属氧中间体的影响对于理解氧化还原反应至关重要.
- 高价金属氧物种的反应性通常通过质子化或易斯酸结合得到增强.
- 铁氧复合物在生物和工业氧化过程中至关重要.
研究的目的:
- 为了研究质子对铁V-oxo复合体与四胺宏环连接体 (TAML) 的作用.
- 描述质子铁{V) -oxoTAML复合物及其结合常数.
- 评估质子化对氧原子转移 (OAT) 和电子转移 (ET) 反应性的影响.
主要方法:
- 单核非血Fe (V) -oxoTAML复合体 (1) 和其质子形式 (2 和 3) 的合成和表征.
- 包括共振拉曼,EXAFS和EPR在内的光谱技术,支持DFT计算.
- 确定质子结合常数和一个电子的还原潜力 (Ered).
主要成果:
- 在TAML联体上发生质子化,形成明确的铁氧物种 (2和3).
- 在硫化硫醇衍生物中观察到极大增速 (高达10^7倍).
- 质子复合体的显著正转变降低潜力 (Ered 2 = 0.97 V 与 0.33 V 的 1).
结论:
- 铁-氧TAML复合物的质子化显著提高了它们在OAT和ET反应中的反应性.
- 硫化机制可以涉及ET或直接OAT,这取决于驱动力.
- 这项工作为高价值金属氧物种的酸调节反应提供了基本的见解.
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