选择性和原子转移的机制由一个可分离的imidoiron (III) 复合体
Ryan E Cowley1, Nathan A Eckert, Sridhar Vaddadi
1Department of Chemistry, University of Rochester, Rochester, New York 14627, USA.
Journal of the American Chemical Society
|May 14, 2011
概括
这项研究研究了铁中原子转移 (HAT) 的研究. 这项研究揭示了对基质大小的强烈依赖,通过硬质控制提供了选择性C-H键激活的潜力.
科学领域:
- 有机金属化学 有机金属化学
- 催化剂是一种催化剂.
- 反应机制 反应机制
背景情况:
- 铁氧复合物及其原子转移 (HAT) 反应得到了充分的记录.
- 铁 - 胺基复合体的理解较少,需要对其HAT能力进行机制研究.
研究的目的:
- 通过可分离的铁 (III) imido复合体,机械地研究原子转移 (HAT).
- 评估添加剂和反应条件对HAT效率和选择性的作用.
- 探索控制CH债券激活选择性的潜力.
主要方法:
- 一个铁 (III) 形状复合体 (L (Me) FeNAd) 的合成和表征.
- 动力和平衡研究以确定反应中间体和速率决定步骤.
- 动态同位素效应 (KIE) 测量 (H/D) 来探测C-H键裂变.
- 添加剂,溶剂极性和碳化合物基质的系统变化.
主要成果:
- 在HAT之前,皮里丁连接体结合,形成一个四坐标中间体.
- 非常大的H/D动态同位素效应 (~100) 表示显著的C-H键裂变.
- HAT速率受到电子和溶剂效应的影响,这表明质子转移特性.
- 观察到HAT比率与碳化合物基质大小的强烈依赖,这归因于硬质障碍.
结论:
- 铁(III) imido复合体经历HAT,具有显著的C-H键裂解特征.
- 体结合和反应条件调节HAT速率和选择性.
- 与观众配体的固体相互作用为控制C-H键激活中的区域选择性提供了一种策略.
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