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铁酶模型的质子化在中异构化后进行
Mioy T Huynh1, David Schilter, Sharon Hammes-Schiffer
1Department of Chemistry, University of Illinois at Urbana-Champaign , Urbana, Illinois 61801, United States.
Journal of the American Chemical Society
|August 6, 2014
概括
铁二甲酸盐的质子突变出乎意料地发生在铁部位,而不是铁键. 这一途径涉及更基本的,以前未被检测到的同位素,影响其他金属复合体和.
科学领域:
- 有机金属化学 有机金属化学
- 无机化学 无机化学 无机化学
- 计算化学是一种计算化学.
背景情况:
- 铁二酸盐在催化过程中很重要.
- 相关金属复合体中的质子化机制尚未完全理解.
- 之前的研究表明,质子化发生在金属对金属键上.
研究的目的:
- 为了研究减少的铁二甲酸盐的质子化路径.
- 为了确定这些复合体中的质子化位点.
- 探索异构体在反应机制中的作用.
主要方法:
- 合成和表征铁二硫酸盐金属复合物的同源序列 (M=Ni,Pd,Pt).
- 电化学研究包括质子化和单电子氧化.
- 密度函数理论 (DFT) 计算用于探测潜在能量表面和同位素.
主要成果:
- -铁复合物的质子化发生在铁位点,形成Fe(0) Ni(II) 同位体,而不是Fe(I) -Ni(I) 键.
- 具有Pd和Pt的同类系列复合物也经历质子化和氧化,形成具有良好的特征的化物和混合价值物种.
- DFT的计算证实了-铁复合体中存在一个更基本的Fe(0) Ni(II) 同位素,它有一个正方形平面的Ni位点.
结论:
- 减少的NiFe二酸盐的质子化通过以前未被检测到的,更基本的Fe{0}Ni{2}) 同位体进行.
- 这一发现挑战了以前关于这些复合体中的质子化位点的假设.
- 发现的途径对理解其他金属复合体和中的质子化有潜在的影响.
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