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在铁复合体中的氧化还原活性化联体之间形成可逆的C-C键
Thomas R Dugan1, Eckhard Bill, K Cory MacLeod
1Department of Chemistry, University of Rochester, Rochester, New York, USA.
Journal of the American Chemical Society
|November 28, 2012
概括
这项研究揭示了铁 (I) 复合物,其中化连接体获得了自旋密度,作为电子储库. 这些配体经历可逆的C-C键形成,储存电子,并使铁具有独特的化学成分.
科学领域:
- 有机金属化学 有机金属化学
- 无机化学 无机化学 有机化学
- 协调化学 协调化学
背景情况:
- 铁复合物与重的配体提供独特的反应性.
- 了解金属连接体系统中的电子分布对于催化是至关重要的.
- 皮里丁连接体可以参与氧化还原过程.
研究的目的:
- 合成和表征新的铁 (I) 复合物.
- 研究这些复合体中的电子结构和旋转密度分布.
- 为了探索协调的皮里丁配体的反应性.
主要方法:
- 合成L(Me) Fe(Py-R) ((2) 复合体. 这些复合体
- 通过X射线晶体学进行结构分析.
- 谱学表征 (例如,EPR,Mössbauer). 这是一个非常简单的方法.
- 密度函数理论 (DFT) 的计算.
主要成果:
- 合成了铁 (I) 复合物与体积大大的β-二甲基胺联体.
- 皮里丁连接物优先接受未配对的自旋密度.
- 这种S = 3/2的物种是Fe (II) /pyridine基和Fe (I) 的共振混合物.
- 未受保护的皮里丁经历可逆基结合 (C-C 键形成).
- 一个合的二铁 (II) 复合体将电子储存在连接体中的C-C键中.
结论:
- 通过C-C键形成在连接体中的电子储存为氧化还原活性连接体提供了一个新的范式.
- 这种可逆的C-C键形成在化连接体中是这些铁复合物的关键特征.
- 这些发现为电子转移机制和催化剂的潜在应用提供了洞察力.
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