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Published on: August 2, 2012
悬挂基作为铁化物和二复合体中的质子继电器
Renee M Henry1, Richard K Shoemaker, Daniel L DuBois
1Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO 80309, USA.
Journal of the American Chemical Society
|March 2, 2006
概括
这项研究详细介绍了铁复合物的两步质子化,揭示了内和外异构体中明显的质子/化物交换行为. 这些发现提供了有关酶酶的质子中继机制的见解.
科学领域:
- 有机金属化学 有机金属化学
- 协调化学 协调化学
- 生物有机化学 生物有机化学
背景情况:
- 铁复合物与素连接体在催化和生物无机化学中至关重要.
- 质子转移机制对酶功能至关重要,特别是在化酶中.
- 了解对金属化物反应性的连接体质子效应是关键.
研究的目的:
- 为了研究一个特定的铁复合物的逐步质子化,转-[HFe(PNP) ((dmpm) ((CH3CN) ]BPh4.
- 为了描述由此产生的质子化物种的质子/化物交换动态.
- 阐明酶酶相关的质子继电机制中的联结体结构和悬挂基的作用.
主要方法:
- 使用不同强度的酸的质子反应 (p-cyanoanilinium tetrafluoroborate,三酸).
- 在低温度 (-80°C) 的NMR光谱 (1H,31P) 在化溶剂 (乙-d6,乙) 中.
- 动力学研究以确定激活障碍和pKa值.
主要成果:
- 质子化产生了跨-[HFe ((PNHP)) ((dmpm)) ((CH3CN)))) ((BPh4) 2.2) 的内和外同体.
- 内分异构体表现出快速的分子内质子/化物交换 (12 kcal/mol激活屏障);外分异构体没有.
- 观察到异构体之间的分子间质子交换,pKa值为12.
- 与三酸进行进一步的质子化形成了二复合体,[{H2Fe}{PNHP}{dmpm}{CH3CN}3+.
- 相关的复合物证实了悬浮基和转配体在交换反应中的重要性.
结论:
- 这项研究表明,铁复合物的不同质子和质子/化物交换途径基于异构.
- 连接体设计,包括悬挂基和转换替代物,显著影响质子继电器效率.
- 这些发现为纯铁化酶的机制提供了宝贵的见解.
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