氧化添加的碳-碳键与一个氧化还原活性 bis ((imino) pyridine铁复合物铁复合物
Jonathan M Darmon1, S Chantal E Stieber, Kevin T Sylvester
1Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14850, USA.
Journal of the American Chemical Society
|October 10, 2012
概括
铁复合物与双胺连接物与双烯反应,形成新的铁双化合物. 这种反应涉及铁和配体的电子损失,产生独特的旋转交叉铁化合物.
科学领域:
- 有机金属化学 有机金属化学
- 协调化学 协调化学
- 材料科学 材料科学 材料科学
背景情况:
- 双胺连接物是协调化学中的多功能支架.
- 铁二化合物是固定研究中的关键中间体.
- 了解氧化还原活性配体对于设计新型功能材料至关重要.
研究的目的:
- 为了研究 bis(imino) pyridine 铁二复合物的与二烯的反应性.
- 为了描述产生的铁二化合物的结构和电子特性.
- 阐明氧化加和电子转移的机制.
主要方法:
- 铁二化合物的合成及其与双烯的反应.
- 用X射线衍射来确定分子结构.
- 莫斯巴乌尔光谱,NMR光谱,磁化学,X射线吸收和X射线发射光谱仪用于电子结构分析.
- 破碎对称密度函数理论 (DFT) 的计算.
主要成果:
- 氧化添加双中的C-C键发生在环境温度下,产生铁双化合物.
- X射线衍射揭示了铁金属循环的正方形金字塔几何形状.
- 谱学和计算研究确定了反铁磁结合的旋转交叉铁基化合物,与bis ((imino) pyridine配体的基离子相结合.
- 反应涉及铁中心和连接体的合作电子损失.
结论:
- 双胺铁复合物很容易经历与二烯的氧化添加.
- 由此产生的化合物表现出复杂的电子结构,具有旋转交叉行为.
- 反应机制突出了金属中心和连接体的合作氧化还原活性.
相关概念视频
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o-hydroxy phenols are oxidized to o-quinones and p-hydroxy phenols to p-quinones. Such redox reactions involve the transfer of two electrons and two protons. The reversible redox property is crucial in...
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