合成铁-硫-碳站点的酶相关反应性
Amy L Speelman1, Ilija Čorić1, Casey Van Stappen2
1Department of Chemistry , Yale University , 225 Prospect Street , New Haven , Connecticut 06520 , United States.
Journal of the American Chemical Society
|August 13, 2019
概括
合成的铁-硫-碳复合物模仿酶活性,使 (N2) 结合并降解为氨和. 催化还原的挑战突出了未来仿生复杂设计的领域.
科学领域:
- 生物有机化学
- 有机金属化学
- 催化剂
背景情况:
- 酶利用铁辅因子 (FeMoco) 的活性位点进行 (N2) 固定.
- 有硫 (S) 和碳 (C) 供体的简单合成化合物可以模仿FeMoco的结合环境.
- 此前,N2结合在S和C捐赠者的单核铁部位实现.
研究的目的:
- 研究合成铁-硫-碳系统中N2结合的机制.
- 了解铁氧化状态在N2协调和减少中的作用.
- 在仿生场所探索N2降解为氨和的可能性.
主要方法:
- 铁酸复合物的合成.
- 使用KC8的电化学还原.
- 包括Mössbauer,EPR和X射线吸收光谱的光谱表征.
- 密度函数理论 (DFT) 的计算.
- 与N2和弱酸发生反应.
主要成果:
- 观察到减少到一个铁 (S=3/2) 和保留的硫协调.
- 进一步降解到铁(0) 诱导了硫酸盐解离和N2结合.
- 将其减少到正规的铁 (I) 状态,然后与酸产生氨和.
- 由于联体质子和解离,催化N2降解没有成功.
结论:
- 在这个系统中,N2的结合和降解需要超越铁的降解状态到铁的降解状态和铁的降解状态.
- 合成Fe-S-C可以从N2中产生酶产物 (氨,).
- 基稳定性对于实现催化N2降低至关重要,为未来的仿生复合设计提供了洞察力.
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